J. Phys. Chem.

A 2005, 109, 9617-9626 9617

Rules for Generating Conformers and Their Relative Energies in n-Alkanes with a
Heteroelement O or S: Ethers and Alcohols, or Sulfides and Thiols

P. Vansteenkiste, E. Pauwels, V. Van Speybroeck, and M. Waroquier*

Center for Molecular Modeling, Laboratory of Theoretical Physics, Ghent UniVersity, Proeftuinstraat 86,
B-9000 Gent, Belgium
ReceiVed: April 13, 2005; In Final Form: August 12, 2005

With the aid of density functional theory calculations, all conformers of several single-chain alcohols, thiols,
ethers, and sulfides are investigated. Starting from earlier computational works on n-alkanes, we construct an
extended set of general rules for predicting the number and occurrence of conformers in these oxygen- or
sulfur-containing compounds. In alcohols and thiols, it is found that only the conformers generated by internal
rotations in the HXCH2CH2CH2 (X ) O or S) top are distinctive from those in n-alkanes. In ethers and
sulfides, the primary influence of the heteroelement also extends up to three internal rotations, but many
more conformers are possible. However, a number of double gauche sequences are forbidden, and therefore,
several conformers can be eliminated. These exclusions in particular make up a set of rules for eventually
deducing all possible conformers. Furthermore, on the basis of only an exact calculation of these gg
conformations in addition to single gauche conformers, it is possible to make an accurate estimate of the
relative energy. This two-dimensional approximation scheme constitutes an effective tool for adequately
describing the relative energies of all possible conformers at a minimal computational cost.

1. Introduction al.5 introduced a general set of rules for predicting the number
and occurrence of conformers in n-alkanes. However, it has not
In this article, we focus on the conformers of four types of
been established whether these rules also apply for similar
single-chain molecules. We choose the heteroelements O and
compounds, such as those of this study.
S for substitution of a CH2 fragment in n-alkanes. The resulting
compounds (ethers and alcohols or sulfides and thiols) are, like In this article, we therefore deduce an additional set of general
n-alkanes, also single-chain molecules, but their energetically rules for the occurrence of conformers in alcohols, thiols, ethers,
most stable structure is not a priori an all-trans conformation. and sulfides. Despite their apparent similarities (O and S are
Furthermore, it is unclear what the geometries and relative situated in the same column of Mendelev’s table), the properties
energies of the different conformers are. of oxygen- or sulfur-containing molecules may vary substan-
The considered molecules are omnipresent in (fine) chemistry tially, and the most important differences and analogies are
and biochemistry,6-15 and are tremendously economically highlighted. In addition, the relative energies of all conformers
important. For a thorough understanding of the (bio)chemical are rigorously determined, and an approximation scheme for
processes in which these molecules are involved, one needs an making reasonable estimates for the relative energies without
accurate description of the conformational flexibility. A micro- the need for explicit ab initio calculations on all conformers is
scopic evaluation of molecular properties mainly depends on suggested.
the knowledge of the various conformers which can be formed, The introduction of general rules for determining the number
and in particular on their relative energies. This is essential, and occurrence of conformers and the availability of a fast
since it is far from certain that the active conformer always method for producing reliable energy estimates for these
corresponds to the global minimum of the potential energy structures constitute an important step forward in tackling long
surface. chain alcohols and thiols or ethers and sulfides. The methodol-
It is well-known that internal rotation about a single C-C ogy presented in this paper can readily be extrapolated to
bond generates a potential energy curve with three local examine other types of single-chain compounds.
minima: one trans (t) and two gauche (g- and g+) conforma-
tions.1-5 Rotation about a single C-O or C-S bond produces 2. Labeling Convention for Conformers
a similar potential energy profile. An easy conclusion would
be that there are 3n conformers for any molecule having n such To unambiguously describe the different conformers, a
(C-C, C-O, or C-S) single bonds. This was shown not to be convenient and consistent labeling system must be introduced.
true for n-alkanes,3-5 and in fact, 3n presents only a lower bound A first step is to specify the conformation of an individual
for the actual number of possible conformers. However, for internal rotation. In Figure 1a, typical potential energy variation
longer molecules with many internal rotations, this number of is shown as a function of the dihedral angle controlling the
conformers grows exponentially, and it becomes almost impos- internal rotation about a C-C bond (this figure does not apply
sible to locate and describe them all. For this reason, Tasi et for internal rotation of ending methyl tops). There are three
minima corresponding to three conformations, labeled by the
* To whom correspondence should be addressed. Telephone: 32 (0)9 indices t, g-, and g+, corresponding to trans, gauche -, and
264 65 59. E-mail: [email protected]. gauche + orientations, respectively. Rotations about a C-O or
10.1021/jp051910b CCC: $30.25 © 2005 American Chemical Society
Published on Web 10/04/2005
9618 J. Phys. Chem. A, Vol. 109, No. 42, 2005 Vansteenkiste et al.

conformer of 1-pentanol is converted to HOg-tg+t. Similarly,

the tSg-g+ conformer in ethyl propyl sulfide is converted into
tSg+g-. As a result, all tabulated conformers, except the all-
trans conformers, correspond to two mirror geometries with the
same electronic energy.

3. Computational Details
Within the class of density functionals, it is well-known that
the hybrid B3LYP and B3PW91 functionals16 have proven to
be a successful approach for obtaining accurate molecular
structures, vibrational frequencies, heats of formation, and bond
energies.17-20 In particular, we have shown in ref 1 that the
triple-ζ 6-311g** basis set in combination with the B3LYP
Figure 1. Example of typical potential energy profiles of internal functional produces reliable potential energy profiles for n-
rotation about a (C)C-C(C) bond (gray line) and a (C)C-O(C) bond alkanes, and for this reason, we select this functional for the
(black line). The three minima are labeled. The reference of the calculations in this work. Although the current set of molecules
(absolute) dihedral angle corresponds with the cis geometry. is very similar to n-alkanes (only one CH2 fragment is replaced
with an O or S atom), this level of theory (in particular, the
basis set) cannot be used without further analysis. As oxygen
and sulfur both have electron lone pairs and are hence likely to
require a more extended basis set and diffuse functions, we have
to select an appropriate basis set to be used in the B3LYP cal-
culations. Moreover, S is a third-period element in Mendelev’s
table for which more polarization functions may be required,
although the 6-311g** basis set (combined with MP2) was
found to be more than adequate for dimethyl sulfoxide.21 In
Figure 2. Illustration of labels used to identify specific internal
this light, the 6-311+G(3df,2p) and 6-311++G(3df,3pd) basis
rotations (with their dihedral angles) in (a) primary alcohols (X ) O) sets will be employed. As these two larger basis sets are
and thiols (X ) S) and (b) ethers (X ) O) and sulfides (X ) S). computationally very demanding, we also add the smaller
6-31+g* basis set to our basis set investigation. This basis set
C-S single bond generate similar potential energy profiles, and has the advantage over the 6-311g** basis set in that it includes
the minima are labeled in a similar way. a diffuse function, and in that it considerably reduces the
When multiple internal rotations within a molecule are computational time. The inclusion of a diffuse function is
considered, the individual conformation of each rotation has to expected to improve the results considerably,22 even more than
be assigned. The appropriate labeling convention for a sequence the addition of polarization functions or improvement of the
of internal rotations in the molecules considered in this paper valence description.
is illustrated in Figure 2. For alcohols and thiols (Figure 2a), For the transparency of the notation, we introduce the short-
the first internal rotation (with dihedral angle φl1) is about the hand acronyms B1 for the 6-31+g* basis set, B2 for 6-311g**,
C-X bond (X ) O or S). The other rotations are labeled as φlx B3 for 6-311+G(3df,2p), and B4 for 6-311++G(3df,3pd).
where x indicates the position of the C-C rotation axis with All calculations are performed with Gaussian9823 and
regard to the C-X bond. Also, the position of the hydroxyl top Gaussian03.24
is written explicitly. For example, the HOg+tg-t conformer of We investigate the combination of the mentioned basis sets
1-pentanol (or HSg+tg-t for 1-pentanethiol) is a shorthand (B1-B4) with B3LYP, and also B3PW91 combined with the
notation for φl1 ) g+, φl2 ) t, φl3 ) g-, and φl4 ) t, where l4 B1 and B4 basis sets, to select the appropriate DFT level of
indicates the ethyl torsion, l3 the propyl torsion, etc. theory. These six approaches are used to evaluate the basis set
For ethers and sulfides, the same convention applies, but one dependence for 1-propanol, 1-propanethiol, methyl propyl ether,
has to distinguish between the two alkyl fragments (Figure 2b). and methyl propyl sulfide which are model compounds for
The subscript l indicates that the rotation is situated in the alcohols, thiols, ethers, and sulfides, respectively. For each of
longest alkyl top on the heteroelement, and the s refers to the these molecules, all conformers are identified and the electronic
shortest alkyl branch. The numbers refer to the position of the energies obtained from full geometry optimizations on these
involved bond with respect to X: 1 specifies the rotation about conformers are compared with each other.
the C-X bond, 2 the consecutive rotation, etc. In general, we In addition to these molecules, also the conformers of methyl
refer to a conformer by specifying the individual conformations ethyl ether (MEE), methyl ethyl sulfide (MES), diethyl ether
in the order φsmax ... φs1Xφl1 ... φlmax (for alcohols and thiols, (DEE), and diethyl sulfide (DES) are calculated at different
there are no s internal rotations, making the above-defined levels of theory. For these molecules, experimental data are
nomenclature a special case of this more general definition), available.
where X ) O or S. For example, in ethyl propyl ether, tOg-g+ Each of the mentioned conformers in this article is found by
is the shorthand notation for φs1 ) t, φl1 ) g-, and φl2 ) g+, performing full, unrestrained geometry optimizations. No
while the same configuration in ethyl propyl sulfide is called potential energy scans or surfaces are employed. An initial set
tSg-g+. of conformer geometries was created, based on the possible
We remark that all molecules in this work are subject to the conformations of a single internal rotation (gauche, trans, etc.).
symmetry operation σh which converts all gauche +/- orienta- The set was then extended by additional sampling of the
tions into its gauche -/+ mirror image. The trans conformations conformations of consecutive internal rotations. Finally, the
are not affected. For example, the above-mentioned HOg+tg-t initial geometries were optimized without any constraints.
Rules for Generating Conformers in n-Alkanes J. Phys. Chem. A, Vol. 109, No. 42, 2005 9619

TABLE 1: Relative Energies without ZPE (in kJ/mol) of the are smaller than the expected accuracy of the B3LYP or
Various Conformers of the Model Compounds 1-Propanol, B3PW91 functionals, and therefore, it is not possible to conclude
Methyl Propyl Ether, 1-Propanethiol, and Methyl Propyl from these data which geometry is the real global minimum.
Sulfidea
Moreover, with the inclusion of zero-point energies (Table 1
B3LYP B3PW91 of the Supporting Information), the HOtt conformer becomes
B1 B2 B3 B4 B1 B4 the lowest-energy conformer for all methods (except B3LYP/
1-propanol B2). The energies of the other conformers increase in the
HOg-g-/HOg+g+ 0.85 0.00 0.68 0.65 0.91 0.67 following order in all methods (except B3LYP/B2): HOtg <
HOg-g+/HOg+g- 1.05 1.23 0.83 0.89 1.07 0.84 HOg-g- < HOg-g+ (with a maximal energy difference of ∼1
HOtg-/HOtg+ 0.39 1.48 0.35 0.21 0.77 0.58 kJ/mol).
HOg-t/HOg+t 0.00 1.19 0.00 0.04 0.00 0.00
HOtt 0.19 2.44 0.11 0.00 0.43 0.22 The B3LYP/6-311g**(B2) results show a slightly different
methyl propyl ether pattern, but we should be careful in drawing conclusions as the
Og-g-/Og+g+ 6.70 6.07 6.35 6.45 6.46 6.34 energy discrepancies are on the order of 2 kJ/mol. Anyway,
Otg-/Otg+ 0.19 0.00 0.02 0.03 0.29 0.15 there are indications that B2 is not the most adequate basis set
Og-t/Og+t 6.33 7.50 6.22 6.30 6.10 6.16 for describing these molecules. This is confirmed by the results
Ott 0.00 1.38 0.00 0.00 0.00 0.00
1-propanethiol predicted for methyl propyl ether (see Table 1). Within the same
HSg-g-/HSg+g+ 2.31 1.63 1.91 1.88 1.96 1.56 level of theory, basis sets B1, B3, and B4 give almost identical
HSg-g+/HSg+g- 2.66 2.20 2.01 1.98 2.52 1.84 results, while the results obtained with the B3LYP/B2 method
HStg-/HStg+ 5.71 5.37 5.23 4.97 5.69 4.83 are deviating for the conformers with φl2 in trans (Og-t/Og+t
HSg-t/HSg+t 0.00 0.00 0.00 0.00 0.00 0.00 and Ott).
HStt 2.92 3.01 2.66 2.43 3.13 2.49
methyl propyl sulfide For both molecules, the results with the B1 basis set show a
Sg-g-/Sg+g+ 1.98 1.22 1.60 1.66 1.49 1.33 very good quantitative agreement with those with the larger B3
Sg-g+/Sg+g- 5.94 5.54 5.88 5.96 6.01 6.06 and B4 basis sets. Additionally, the geometries of the conformers
Stg-/Stg+ 2.83 2.84 2.56 2.51 2.60 2.27 optimized with B1 are almost identical to the B3 and B4
Sg-t/Sg+t 0.08 0.00 0.17 0.32 0.05 0.39 geometries, while the B2 geometries are somewhat divergent.
Stt 0.00 0.40 0.00 0.00 0.00 0.00
a The conformer with the lowest electronic energy is taken as a
We now discuss the relative energy values for the conformers
of the sulfur compounds 1-propanethiol and methyl propyl
reference. The basis sets are defined as follows: B1 ) 6-31+g*, B2
) 6-311g**, B3 ) 6-311+G(3df,2p), and B4 ) 6-311++G(3df,3pd).
sulfide (Table 1). In contrast with oxygen compounds, the
influence of the selected basis set is rather limited, and the B2
set produces results that are comparable with the B1 values.
Basis Set Dependence. As a primary task, the basis set
As B1 is somewhat faster than B2, and because we wish to use
dependence of the B3LYP (B3PW91) functional for alcohols,
the same level of theory for both oxygen and sulfur compounds,
thiols, ethers, and sulfides is studied. One of the principal aims
the B1 basis set still has a preferential status.
of this study is the selection of a cost-effective level of theory
that still produces accurate results. For this reason, we apply The above discussion supports the preference of basis set
only the B3LYP and B3PW91 functionals in the DFT calcula- 6-31+g*(B1) to basis set 6-311g**(B2) for DFT/B3LYP
tions. We use two “small” basis sets (B1 and B2) and two more calculations on the selected set of molecules, but a validation
extended basis sets (B3 and B4). The latter basis sets are used with experimental data is needed to draw final conclusions about
to calculate the reference energy differences. The values the most suitable basis set.
predicted by the smaller B1 and B2 sets can then be compared The smallest alcohol of our set of molecules for which
with these reference values. experimental data are available is ethanol. Several experimental
Four reference molecules are chosen to represent the different papers have reported that the trans conformer in this molecule
classes of molecules that are studied: 1-propanol (alcohols), is slightly more stable than its gauche conformer. Depending
methyl propyl ether (ethers), 1-propane thiol (thiols), and methyl on the experimental methods, the measured energy differences
propyl sulfide (sulfides). Each of these molecules shows two vary from 0.49 kJ/mol for microwave spectroscopy25 to 1.31
single bonds about which an internal rotation can generate kJ/mol for gas-phase Raman spectroscopy26 and to 2.9 kJ/mol
different conformations, and forms the smallest compound of for overtone spectroscopy.27 Also on the theoretical level, a lot
each class to have more than two energetically different of work has been done.28 For example, a recent study of Weibel
conformers. In accordance with the labeling convention, these et al.29 gives an interesting overview of several theoretical results
rotations are identified as φl1 and φl2, each rotation covering on this trans-gauche energy difference. A correct theoretical
three conformations (t, g-, and g+). Combination of these prediction of the trans form as the most stable conformer is not
geometries leads to a total of nine conformers. Due to the σh uniformly obtained, and is very sensitive to the level of theory
symmetry, this number is reduced to five sets of energetically used. The assignation of the lowest-energy conformer can even
different conformers: Xtt, Xg-t/Xg+t, Xtg-/Xtg+, Xg-g-/Xg+g+, change by inclusion of zero-point energy (ZPE). In this work,
and finally Xg-g+/Xg+g- [X ) (H)O or (H)S]. The latter set the B3LYP/6-31+g*(B1) results favor the trans conformer by
of conformers is a result of the combination of gauche standings 0.27 kJ/mol (no ZPE included). The predicted energy difference
with different orientations. Only for methyl propyl ether could is rather small, but acceptable.
no such Og-g+/Og+g- conformer be found. More recently, Takahashi et al.30 performed a DFT calculation
Table 1 shows the relative energies of the different conformers on the B3LYP/6-311++G(3df,3pd)(B4) level of theory, result-
of 1-propanol. The most stable conformer at each level of theory ing in an energy difference of 0.41 kJ/mol in favor of the trans
is the reference for the potential energy differences. Except for conformer in ethanol, with inclusion of ZPE. They also reported
the B3LYP/6-311g**(B2) level, all other levels of theory energy differences (including ZPE contributions) on the same
attribute the global minimum to either the HOtt or HOgt level of theory between the conformers of 1-propanol. They
conformer. The energy difference between these two types of predict that the all-trans conformer is the most stable conformer,
conformers is quite small (0.4 kJ/mol at most). These differences followed by the HOtg and HOgt conformers with a maximal
9620 J. Phys. Chem. A, Vol. 109, No. 42, 2005 Vansteenkiste et al.

TABLE 2: Relative Energies (in kJ/mol) of the Various

Conformers of the Compounds Methyl Ethyl Ether, Methyl
Ethyl Sulfide, Diethyl Ether, and Diethyl Sulfide Compared
with Experimenta
B3LYP
B1 B2 B3 B4 experiment refs
methyl ethyl ether
Og 6.48 6.14 6.35 6.48 4.6 f 6.3 31, 32
methyl ethyl sulfide
Og 0.57 0.07 0.46 0.67 -0.8 f 1.5 31, 33
diethyl ether
g-Og-/g+Og+ 12.70 11.33 12.47 12.71
g-Og+/g+Og- 16.21 15.49 16.04 16.27
tOg-/tOg+/g-Ot/g+Ot 6.60 6.13 6.42 6.59 4.81 34
tOt 0.00 0.00 0.00 0.00 0.00 34
diethyl sulfide
g-Sg-/g+Sg+ 1.14 0.15 0.82 1.15 ≈0 35
g-Sg+/g+Sg- 4.47 3.73 4.38 4.78 large 35
tSg-/tSg+/g-St/g+St 0.69 0.24 0.52 0.73 ≈0 35
tSt 0.00 0.00 0.00 0.00 small 35
a The basis sets are defined as follows: B1 ) 6-31+g*, B2 )

6-311g**, B3 ) 6-311+G(3df,2p), and B4 ) 6-311++G(3df,3pd).

energy difference of merely 0.25 kJ/mol. The HOg-g- and Figure 3. Newman projections of the typical dihedral angle values
HOg-g+ geometries are 0.8 and 1.2 kJ/mol higher in energy, for gauche g, slightly distorted gauche x′, and distorted gauche x around
respectively, than the HOtt reference. These results almost a (a) C-C, (b) C-O, and (c) C-S single bond.
coincide with the values reported in this work (see Table 1 of
the Supporting Information), except for the B3LYP/B2 level In this study, we evaluate the geometries of the conformers
of theory. of alcohols, thiols, ethers, and sulfides. The possible interactions
Other available experimental and/or ab initio data are very between consecutive internal rotations will be investigated, and
scarce, and are collected in Table 2. The agreement between the occurrence of distorted gauche conformations x will be
experiment and the theoretical calculations is very satisfactory. examined. On the basis of these findings, we will introduce a
Finally, this basis set investigation allows us to conclude that complementary set of rules which allows the determination and
the B3LYP/6-31+g*(B1) level is the best cost-effective level structural identification of the total number of conformers in
of theory for use in all further calculations. these compounds at a minimal computational expense. In
addition, we also calculate the relative energies of the different
4. Conformational Analysis conformers and compare these to the corresponding values in
The different conformers of n-alkanes are reached by n-alkanes.
performing internal rotations about the C-C bonds apart from 4.1. Alcohols. Since primary alcohols are n-alkanes in which
the methyl tops. Each rotational profile is characterized by three a methyl top has been replaced with an OH group, similar
distinct potential energy minima (as shown in Figure 1, t, g+, conformations can be expected to occur, especially for rotations
and g-). Obviously, one could expect that a molecule with n about bonds that are far from the hydroxy group. Table 3
such internal rotations would lead to 3n conformers. displays the relative electronic energy of a selection of conform-
In several papers, the occurrence of conformers in n-alkanes ers from ethanol to 1-hexanol, determined at the B3LYP/6-
was studied.3-5 The most extensive study was performed by 31+g* level of theory. The conformers are arranged according
Tasi et al.5 They reported the existence of distorted gauche to the labeling convention for the five rotations φl1-φl5, even
standings x, for which the typical dihedral angle has a value of when the involved primary alcohol has fewer than five internal
approximately (85°, or 95° from trans, while normal gauche rotations. For instance, the notation HOg+g-(ttt) refers to the
standings in n-alkanes have a dihedral of (65°, or 115° from HOg+g-ttt conformer in 1-hexanol, HOg+g-tt in 1-pentanol,
the trans conformation (Figure 3a). The combination of these HOg+g-t in 1-butanol, and the HOg+g- conformer in
five possible conformations leads to 5n conformers. The actual 1-propanol. No energy value for ethanol is given, since only
number of conformers lies between 3n and 5n, since the distorted the φl1 rotation is available in this molecule.
gauche conformations exist under only special circumstances. Table 3 is divided into two parts. The first part treats
In particular, the x-gauche conformations are found in n-alkanes conformers with one or more gauche standings in the φl1-φl3
when two consecutive internal rotations reside in gauche internal rotations, while the φl4 and φl5 dihedral angles remain
standings of the opposite orientation. This g-g+ combination in trans. The second part shows the conformers with one or
brings two carbon atoms close to each other, forcing the carbon more gauche conformations in the latter three φl3-φl5 rotations,
backbone to relax. This relaxation was also observed by the now with φl1 and φl2 in trans. It is clear that these latter
authors for n-pentane and n-hexane2,3 in their study of coupled conformers have geometries and relative energy differences that
internal rotations. On the two-dimensional potential energy are in accordance with those of alkane fragments (see ref 5).
profiles of consecutive internal rotations, two local minima were The relative energies of the HOtttg(t) and HOttttg conformers
identified around the g-g+ geometry, corresponding to x-g+ in 1-pentanol and 1-hexanol amount to almost 4 kJ/mol, which
and g-x+ conformers. The relative energy associated with these is approximately the typical value of 3.9 kJ/mol found in
conformers was found to be considerably higher than those of n-alkane conformers with one gauche standing (at the B3LYP/
the conformers with consecutive gauche standings of the same 6-31+g* level of theory). Alcohol conformers with consecutive
orientation (g-g-/g+g+). gauche standings of the same orientation in the φl3-φl5 part of
Rules for Generating Conformers in n-Alkanes J. Phys. Chem. A, Vol. 109, No. 42, 2005 9621

TABLE 3: Relative Energies (in kJ/mol) of Selected g-g- conformers, due to the occurrence of a slightly distorted
Conformers of Primary Alcohols (at the B3LYP/6-31+g* (x′) or fully distorted (x) gauche conformation (Figure 3a).
level of theory)a However, in this part of the alcohols, only one conformer is
φl1φl2φl3φl4φl5 ethanol 1-propanol 1-butanol 1-pentanol 1-hexanol present around the g-g+ geometry, in contrast to the double
HOCH2CH2CH2 Functional Group Conformers minima typical for n-alkanes. Depending on the value of the
HOt(tttt) 0.00 0.19 0.10 0.10 0.10 φl1 dihedral angle, their structures become HOtg-x′+(tt),
HOg-(tttt) 0.27 0.00 0.00 0.00 0.00 HOg-g-x′+(tt), and HOg+x-g+(tt). The latter conformer has the
HOtg-(ttt) 0.39 0.00 0.13 0.08 most distorted geometry (φl2 ) x) and also has the highest
HOg-g-(ttt) 0.85 0.61 0.76 0.76
HOg+g-(ttt) 1.05 0.80 0.75 0.71 relative energy (∼9 kJ/mol). Still, this is significantly lower
HOttg-(tt) 4.22 4.30 4.26 than the corresponding energy difference in n-alkanes.
HOg-tg-(tt) 4.26 4.25 4.24 The net result of these interactions is that the HOCH2CH2CH2
HOg+tg-(tt) 3.82 3.83 3.80 top of primary alcohols does not obey the typical behavior of
HOtg-g-(tt) 3.42 3.69 3.57
HOg-g-g-(tt) 3.68 3.91 3.78
n-alkanes, as summarized by Tasi et al.5 At the B3LYP/6-31+g*
HOg+g-g-(tt) 4.83 5.10 4.96 level of theory, the first 14 conformers in Table 3 are identified
HOtg-x′+(tt) 7.00 6.95 7.08 as being specific for the φl1 f φl3 internal rotations. Hence,
HOg-g-x′+(tt) 7.14 7.09 7.11 they must be considered as an extension of Tasi’s rules for
HOg+x-g+(tt) 9.20 8.97 8.75 primary alcohols, and an exact description of these alcohol
Alkane-like Conformers conformers is required. However, the relative energies in Table
HOtttg-(t) 4.01 3.92 3 do not vary largely when the chain length is increased, as the
HOttg-g-(t) 7.98 8.06 geometries of the different conformers are practically not
HOttx-g+(t) 13.66 13.43
HOttg-x+(t) 14.16 13.88 affected (Table 2 of the Supporting Information). We may
HOttttg- 4.15 therefore conclude that the 14 functional group conformers as
HOttg-tg- 8.16 given in Table 3 may serve as a suitable, valuable data set for
HOttg-tg+ 8.61 the determination of all conformers in long primary alcohols.
HOtttg-g- 7.52
HOtttx-g+ 14.67
4.2. Thiols. A similar analysis has been done for ethanethiol
HOtttg-x+ 14.69 to 1-hexanethiol. As in alcohols, the influence of the SH end
a The conformer with the lowest binding energy is taken as a
group only has a limited range. The conformers found by the
three rotations in the HSCH2CH2CH2 top (φl1-φl3) determine
reference.
the specific functional group behavior of the thiol and are
presented in Table 4 (with φl4 and φl5 both in trans). The
the molecule [HOttg-g-(t) and HOtttg-g-] have an energy of
conformers resulting from internal rotations further from the
∼8 kJ/mol, which is merely twice the energy value for the single
heteroelement exhibit typical alkane-like behavior. The results
gauche conformers. The energy of the HOttg-tg- and HOttg-tg+
for these rotations are supplied in the Supporting Information
conformers is also in accordance with this summing rule. For a
(Table 3) and are not further discussed.
g-g+ sequence, steric hindrance comes into play. As in
n-alkanes, this g-g+ geometry actually corresponds to a transi- The most striking difference with alcohols is that the various
tion state between two energy minima, each with one distorted thiol conformers are energetically more distinct from each other.
gauche conformation: g-g+ f g-x+ and x-g+. The energy of The HSg-(tttt) conformer systematically has the lowest energy,
these conformers cannot be deduced by simply adding the and all other thiol conformers are at least 2 kJ/mol higher in
energies of the conformers with only one gauche. The steric energy. We have condensed all calculated data in Table 5, where
hindrance causes an energy increase, varying between 5.5 and relative energies are presented with reference to the HSg-tttt
6.5 kJ/mol in excess of the earlier value of 8 kJ/mol. These conformer as well as the HSttttt conformer. Each 〈∆E〉 value
additional energy values are close to the ab initio values in represents an averaged energy difference over all thiol conform-
n-hexane.3 ers corresponding to a specific conformational class. The
The conformers with one or more gauche standings in the shorthand notation g can refer to either a g, an x, or an x′
φl1-φl3 part of the alcohol sequence seem to have a particular conformation. For example, the 14.74 kJ/mol energy difference
behavior, in contrast with the alkane-like behavior of the φl3- of the HSg(g-g+tt conformational class with respect to the
φl5 interactions. The all-trans conformer and the conformers with HSg-tttt reference is an average over the relative energies of
only one gauche for either φl1 or φl2 have approximately the the HSg-x′-x′+(tt), HSg-g-x+(tt), HSg+g-x+(tt), and HSg+x-g+(tt)
same energy. For all alcohols, the reference conformer is conformers of 1-butanethiol, 1-pentanethiol, and 1-hexanethiol.
HOg(tttt), except for ethanol, where the all-trans conformer has Several main characteristics and rules applicable to thiol
the lowest energy. A g-g- or g+g- sequence for the φl1 and φl2 conformers can be extracted from this table in a transparent
rotations results in a slightly higher energy value, but this still way:
remains below 1 kJ/mol. Apparently, the φl3 rotation, and its (i) The energy increase due to a single gauche standing in
interaction with the other internal rotations in the HOCH2- one of the torsions φli when i > 1 is almost independent of the
CH2CH2 top, mainly determines the electronic energy. The conformation for φl1. Only a small discrepancy of ∼0.2 kJ/mol
HOttg(tt) conformers have relative energies of 4.25 kJ/mol on is noticed between the HStg-ttt (with respect to the HSttttt
average. These energies are not significantly altered by an reference) and HSg(g-ttt conformational classes (with respect
additional gauche (g+ or g-) standing in φl1. Hence, the to the HSg-tttt reference). One easily concludes that the
interaction of the φl3 and φl1 internal rotations can be considered conformational interaction of φl1 with the other torsional motions
negligible. A small stabilization is observed for the HOtg-g-(tt) is rather small.
and HOg-g-g-(tt) conformers. This interaction between φl2 and (ii) In general, the above rule is also valid when multiple
φl3 becomes more apparent when these internal rotations assume gauche standings are present in the conformer. The average
gauche conformations of the opposite orientation (g-g+). The relative energies for the HSg(g-g-tt and HStg-g-tt conforma-
relative energies become significantly higher than the φl2φl3 ) tional classes, for example, differ by only some 0.2 kJ/mol.
9622 J. Phys. Chem. A, Vol. 109, No. 42, 2005 Vansteenkiste et al.

TABLE 4: Relative Energies (in kJ/mol) of Some Conformers in Primary Thiols (at the B3LYP/6-31+g* level of theory)
φl1φl2φl3φl4φl5 ethanethiol 1-propanethiol 1-butanethiol 1-pentanethiol 1-hexanethiol
HSt(tttt) 2.37 2.92 2.75 2.72 2.72
HSg-(tttt) 0.00 0.00 0.00 0.00 0.00
HStg-(ttt) 5.71 5.44 5.51 5.46
HSg-g-(ttt) 2.31 2.44 2.53 2.53
HSg+g-(ttt) 2.66 2.65 2.66 2.62
HSttg-(tt) 6.60 6.78 6.77
HSg-tg-(tt) 4.07 4.22 4.22
HSg+tg-(tt) 3.66 3.87 3.84
HStg-g-(tt) 8.35 8.57 8.50
HSg-g-g-(tt) 5.51 5.76 5.64
HSg+g-g-(tt) 6.14 6.43 6.28
HStx′-x′+(tt) 15.17 15.28 15.25
HSg-x′-x′+(tt) 14.22
HSg-g-x+(tt) 14.16 13.96 13.96
HSg+g-x+(tt) 15.48 14.97 15.11
HSg+x-g+(tt) 15.33 15.14 15.10

TABLE 5: Schematic Overview of the Different Classes of rotations in the thiol functional group. In 1-butanethiol, one
Conformers in Thiols (at the B3LYP/6-31+g* level of additional conformer is found (HSg-x′-x′+).
theory)a
4.3. Ethers. In this section, the different conformers in a series
〈∆E〉 of eight ethers are discussed: methyl ethyl ether (MEE), methyl
reference conformational class alkane reference propyl ether (MPE), methyl butyl ether (MBE), methyl pentyl
HSg(g-ttt HSg(tg-tt HSg(ttg-t gttg-t ether (MPeE), diethyl ether (DEE), ethyl propyl ether (EPE),
HSg-tttt 2.55 3.98 3.85 3.94 gtttt ethyl butyl ether (EBE), and dipropyl ether (DPE).
HSttttt 2.75 3.99 3.84 3.96 ttttt Whereas in alcohols or thiols it was possible to list all
HStg-ttt HSttg-tt HStttg-t tttg-t conformers and their calculated energies, this would present an
HSg(g-g-tt HSg(tg-g-t HSg(ttg-g- gttg-g- inefficient approach to examining ethers (or sulfides). Their
HSg-tttt 5.96 7.83 7.61 7.80 gtttt
HSttttt 5.74 7.68 7.51 7.82 ttttt functional group is not an end group, and the influence of the
HStg-g-tt HSttg-g-t HStttg-g- tttg-g- heteroelement can extend to both sides of the molecule. As a
HSg(g-g+tt HSg(tg-g+t HSg(ttg-g+ gttg-g+ result, a considerably larger number of conformers must be
HSg-tttt 14.74 14.02 14.66 14.66 gtttt studied. Ethyl butyl ether, for example, is characterized by four
HSttttt 12.50 14.00 14.61 14.65 ttttt internal rotations and gives rise to at least 34 (81) conformers.
HStg-g+tt HSttg-g+1 HStttg-g+ tttg-g+
A more functional approach is to subsequently examine
a The energy differences 〈∆E〉 (in kJ/mol) with respect to the
conformers with one single, two consecutive, and three consecu-
displayed reference conformer are average values over several thiols tive gauche conformations, and to deduce some general rules
and over various gauche orientations in the same class. Corresponding which apply to all possible ether conformers.
energy differences are also given for alkanes.
Additionally, we will evaluate two approximation schemes
on the basis of their ability to produce reasonable estimates of
Moreover, the energy of the HSg-g-g-(tt) and HSg+g-g-(tt)
the relative energy of a conformer, based on minimal confor-
conformers in Table 4 is virtually independent of a g- or g+
mational data.
conformation for φl1. The only exception to this rule occurs for
4.3.1. Conformers with a Single Gauche. A summary of the
the HSg(g-g+tt conformational class, where notably higher
results for the conformers with a single gauche conformation
average energy values are obtained in comparison with those
in ethers is given in Table 6. The table lists the energy
of the HStg-g+tt class. Here, φl1 does interact with φl2 and
differences relative to the all-trans conformer of the molecules
influences the relative energy.
along with absolute dihedral angles. A gauche conformation
(iii) Sequences with two consecutive gauche standings of the for a dihedral angle alongside the oxygen (φl1 or φs1) results in
opposite orientation in positions φli and φli+1 when i > 1 cause an energy increase of ∼6.5 kJ/mol for ethyl tops, and ∼6.3 kJ/
large interactions (up to 15 kJ/mol) and give rise to double mol for longer alkyl chains. This is quite in contrast to n-alkanes,
minima around the g-g+ maximum. So, starting from φl2 and in which a single gauche conformation causes an energy increase
φl3, consecutive internal rotations interact. However, only for of ∼3.9 kJ/mol at the B3LYP/6-31+g*(B1) level of theory [at
1-butanethiol does this specific interaction result in four different the B3LYP/6-311g**(B2) level of theory, this is 3.6 kJ/mol].
conformations: HSg-x′-x′+(tt), HSg-g-x+(tt), HSg+g-x+(tt), Furthermore, the corresponding dihedral angles of normal
and HSg+x-g+(tt) (Table 4). In 1-pentanethiol and 1-hexanethiol, gauche conformations about the C-C-O-C dihedrals in ethers
the HSg-x′-x′+(tt) conformer does not occur. assume values in the range of 75-77° (Figure 3b). This is much
(iv) The influence of the thiol functional group is virtually larger than the typical dihedral angle of 65° in n-alkanes and
negligible from the φl4 torsion on. This is suggested in the table rather resembles the x′-gauche angle of a C-C-C-C dihedral
as the average energies seem to converge to those found in (Figure 3a). A gauche standing in the next neighboring internal
n-alkanes. rotation alongside the oxygen (φl2 or φs2) causes a conformer
The HSCH2CH2CH2 top in thiols also does not meet the almost as stable as the all-trans conformer, with dihedral angles
typical behavior of n-alkanes. This result is similar to that in of 64°. Note that this applies for ethers as well as alcohols,
alcohols, but here interaction effects between the internal where the φl2 single gauche conformer has the same energy as
rotations are more apparent, which gives rise to energetically the all-trans conformer. Further from the oxygen, the values
distinct conformers. In all compounds, 15 conformers are seem to “relax” to the n-alkane situation: angles of ∼65° and
identified that uniquely characterize the φl1 f φl3 internal relative energies of 4 kJ/mol for φl3 and 3.8 kJ/mol for φl4.
Rules for Generating Conformers in n-Alkanes J. Phys. Chem. A, Vol. 109, No. 42, 2005 9623

TABLE 6: Conformers of Various Ethers and Sulfides with TABLE 7: Conformers of Various Ethers and of EBS with
One Gauchea Two Consecutive Gauche Standingsa
con- con-
former MEE MPE MBE MPeE DEE EPE EBE DPE (φA,φB) former molecule V2D
AB φA φB ∆E1D-est
AB ∆φA ∆φB
gtOtttt 0.22 V1D
s2
(φs1,φl1) x-Ox- DEE 12.70 86.0 86.0 13.20 10.7 10.7
63.7 φs2 EPE 12.20 86.6 88.3 12.72 11.4 11.1
EBE 12.24 86.6 87.4 12.92 11.4 10.3
tgOtttt 6.60 6.42 6.53 6.24 V1D
s1
DPE 11.69 88.3 88.2 12.48 11.6 11.5
75.3 75.2 75.2 76.7 φs1
x-Ox+ DEE 16.21 91.8 -91.8 13.20 16.5 16.5
ttOgttt 6.48 6.33 6.28 6.25 6.60 6.30 6.39 6.24 V1D
l1 EPE 15.67 91.9 -92.3 12.72 16.7 15.1
74.8 76.4 76.7 75.9 75.3 77.2 77.1 76.7 φl1 EBE N/A N/A N/A 12.92 N/A N/A
ttOtgtt 0.19 -0.07 0.01 0.24 0.02 0.22 V1D
l2 DPE N/A N/A N/A 12.48 N/A N/A
63.6 64.1 64.4 63.8 64.3 63.7 φl2 (φl1,φl2) Og-g- MPE 6.70 75.3 59.1 6.52 -1.1 -4.5
ttOttgt 3.99 4.02 4.03 V1D MBE 6.57 75.7 60.1 6.21 -1.0 -4.0
l3
66.0 65.8 66.1 φl3 MPeE 6.52 75.8 60.2 6.25 -0.1 -4.2
EPE 6.90 75.2 59.3 6.54 -2.0 -4.5
ttOtttg 3.83 V1D
l4 EBE 6.58 76.3 60.5 6.41 -0.8 -3.8
65.2 φl4 DPE 6.75 74.9 58.7 6.46 -1.8 -5.0
(φl2,φl3) Otg-g- MBE 3.37 61.5 65.2 3.92 -2.6 -0.8
con- MPeE 3.56 61.5 65.6 4.02 -2.9 -0.2
former MES MPS MBS MPeS DES EPS EBS DPS EBE 3.37 61.5 64.6 4.04 -2.8 -1.5
gtStttt 2.75 V1D Otg-x′+ MBE 6.93 69.8 -74.8 3.92 5.7 8.8
s2
66.2 φs2 MPeE 6.82 69.6 -75.3 4.02 5.2 9.5
EBE 7.19 69.9 -75.8 4.04 5.6 9.7
tgStttt 0.69 0.62 0.63 0.02 V1D
s1 (φl3,φl4) Ottg-g- MPeE 7.74 64.0 61.8 7.85 -1.8 -3.4
72.3 72.6 72.8 73.1 φs1 Ottg-x+ MPeE 13.81 65.7 -87.3 7.85 0.1 22.1
ttSgttt 0.57 0.08 0.20 0.16 0.69 0.17 0.27 0.02 V1D
l1 Ottx-g+ MPeE 13.52 97.4 -63.7 7.85 31.6 -1.5
70.0 72.5 71.4 71.7 72.3 74.1 73.2 73.1 φl1
(φs1,φl1) g-Sg-tt EBS 0.96 72.4 73.0 0.91 -0.4 -0.2
ttStgtt 2.83 2.70 2.66 2.80 2.64 2.75 V1D
l2 g-Sx+tt 3.94 73.3 -97.3 0.91 0.5 24.1
65.9 66.5 66.1 65.7 65.8 66.2 φl2 x-Sg+tt 4.03 96.1 -74.4 0.91 23.3 1.2
ttSttgt 3.80 3.91 3.79 V1D
l3 (φl1,φl2) tSg-g-t EBS 2.21 76.3 67.1 2.91 3.1 1.3
65.4 65.9 65.3 φl3 tSx-g+t 5.37 97.1 -66.2 2.91 23.9 0.4
ttStttg 3.80 V1D
l4 (φl2,φl3) tStg-g- EBS 5.58 62.5 60.7 6.42 -3.3 -4.6
65.5 φl4 tStx′-x′+ 12.02 75.7 -76.4 6.42 9.9 11.1
a Relative energies are given in kJ/mol and absolute dihedral angles
a Relative energies in kJ/mol and absolute dihedral angles in degrees
(at the B3LYP/6-31+g* level of theory). The reference is the all-trans in degrees (at the B3LYP/6-31+g* level of theory). The reference is
conformer. the all-trans conformer. N/A means that the conformer is not present.
∆E1D-est
AB is defined in eq 1.
In conclusion, the nearest (φl1 and φs1) and next-nearest (φl2
When the gauche standings take place at either side of the
and φs2) internal rotations show a behavior which is distinctly
oxygen (gOg), ∆φ angles can amount to g10°. This is mainly
different from that of n-alkanes. For rotations which are further
due to the strong interaction existing between the φs1 and φl1
distanced from the oxygen atom, the alkane-like behavior seems
torsions, manifesting in strongly distorted gauche positions (φ
to be restored.
≈ 90°). Those gauche positions with opposite orientations
4.3.2. Two ConsecutiVe Gauche Standings. All possible ether
(x-Ox+) exhibit very shallow minima and give no evidence for
conformers with two consecutive gauche orientations are listed
a double minimum. They are only detected in smaller ethers
in Table 7. For each conformer, the energy (V2D AB) is given DEE and EPE at the B3LYP/B1 level of theory. At the B3LYP/
relative to the all-trans conformer. In addition, the two corre- B2 level, this minimum is observed in only DEE. In addition,
sponding dihedral angles (φA and φB) are given. In the their relative energies are underestimated by some 3 kJ/mol in
supposition of noninteracting internal rotations, it would be the one-dimensional approximation. The minima corresponding
possible to make a rough guess of these relative energies and with equal orientation (x-Ox-) are more pronounced and occur
dihedral angles using the data of single gauche conformers in all investigated ethers. The relative energies are described
(Table 6). This energy estimate corresponding to two consecu- well within the one-dimensional approach, but evidently, the
tive gauche standings would then be gauche dihedral angles deviate substantially.
Conformers with two consecutive gauche standings alongside
∆E1D-est
AB ) V1D
A (φA ) gA ) + VB (φB ) gB )
1D 1D 1D
(1) the oxygen (Ogg) occur only when both φl1 and φl2 assume
equivalent gauche orientations. Their properties are rather well
where V1D A is the relative energy obtained in a one-dimensional predicted in the one-dimensional approximation: ∆E1D-est AB
approach corresponding to a gauche orientation in torsional closely resembles V2DAB, and ∆φA and ∆φB values are small.
angle φA. g1D A refers to the gauche angle in the single gauche When the two consecutive gauche standings are moved one
conformer, and this dihedral generally differs from the corre- torsion further (Otgg), the typical n-alkane-like pattern already
sponding angle in the conformer with two consecutive gauche begins to manifest. The Otg-g- conformers reveal dihedral
orientations. In Table 7, the difference between both angles angles that are very close to the typical undisturbed value of
(∆φA) is presented along with the one-dimensional energy guess 65°. But, as in the preceding case, two consecutive gauche
(∆E1D-est
AB ). However, it is clear from the previous discussions standings with the opposite orientation do not yet give rise to
that the interaction between consecutive internal rotations is not the double conformational minimum. Instead, only one Otg-x′+
negligible. This was thoroughly confirmed on n-alkanes in refs conformer is found with a slightly distorted φl3 gauche angle.
3 and 5. Still, it is valuable to discuss double gauche conformers A similar effect was observed in alcohols [e.g., the HOtg-x′+(tt)
in terms of their differences with a one-dimensional approach. type conformer in Table 3].
9624 J. Phys. Chem. A, Vol. 109, No. 42, 2005 Vansteenkiste et al.

TABLE 8: Conformers of Various Ethers and of EBS with Three Consecutive Gauche Standingsa
3D 1D-est 2D-est
(φA,φB,φC) conformer molecule VABC φA φB φC ∆EABC ∆EABC
(φs1,φl1,φl2) x-Ox-g- EPE 12.83 86.4 87.7 61.7 12.96 12.80
EBE 12.53 86.4 87.6 62.3 12.94 12.44
DPE 12.32 88.0 87.4 61.5 12.70 12.20
(φl1,φl2,φl3) Og-g-g- MBE 9.82 73.8 56.2 64.3 10.20 10.01
MPeE 9.84 73.2 56.1 65.2 10.27 10.07
EBE 9.87 74.9 56.6 63.9 10.43 9.94
Og-g-x′+ MBE 13.18 76.9 66.9 -74.0 10.20 13.57
MPeE 12.90 76.2 66.1 -75.3 10.27 13.33
EBE 13.37 77.8 68.1 -72.5 10.43 13.76
(φl2,φl3,φl4) Otg-g-g- MPeE 7.31 60.7 63.3 63.1 7.85 7.28
Otx′+g-g- 10.14 73.5 -68.9 -62.9 7.85 10.54
Otx′-g+x- 17.53 78.8 -67.4 88.8 7.85 16.61
Otg-x-g+ 14.17 65.3 93.6 -65.1 7.85 13.06
Otg-g-x+ 14.49 59.7 62.9 -92.5 7.85 13.35
(φs1,φl1,φl2) g-Sg-g-t EBS 2.89 73.3 75.2 66.3 3.58 2.77
g+Sx-g-t 5.40 -70.2 101.5 66.6 3.58 5.88
g-Sx-g+t 6.03 75.6 100.1 -67.1 3.58 6.06
(φl1,φl2,φl3) tSg-g-g- EBS 5.57 72.9 62.4 63.9 6.70 5.15
tSx+g-g- 9.91 -98.7 66.8 66.3 6.70 8.31
tSx-g+x- 17.94 95.9 -68.4 90.5 6.70 14.75
tSg-x-g+ 13.42 79.4 86.6 -67.4 6.70 11.59
tSg-g-x+ 13.66 70.7 66.7 -88.8 6.70 11.59
a Relative energies in kJ/mol and absolute dihedral angles in degrees (at the B3LYP/6-31+g* level of theory). The reference is the all-trans

conformer.

Finally, when the consecutive gauche conformations are energy is estimated as

farther from the oxygen (e.g., φl3φl4 in MPeE), the same behavior
ABC ) VAB(φA ) gA , φB ) gB ) +
∆E2D-est 2D 2D 2D
is revealed as in n-alkanes with the double Ottg-x+ and Ottx-g+
BC(φB ) gB , φC ) gC ) - VB (φB ) gB ) (2)
V2D
minima around the Ottg-g+ maximum. 2D 2D 1D 1D
4.3.3. Three ConsecutiVe Gauche Standings. The number of
ether conformers with three consecutive gauche conformations which is merely an extrapolation of eq 1. This estimate is also
is rather limited (Table 8) as the restrictions on two consecutive given in Table 8 compared to the one-dimensional guess
gauches also seem to apply for three successive gauche ∆E1D-est 3D
ABC . The calculated energy VABC is given relative to the
standings. The g-g+ conformation never appears for the φs1φl1 all-trans conformer.
and φl1 and φl2 dihedral angles. This implies that only the The energies of the triple gauche conformers exhibit large
x-Ox-g- conformer is formed in the φs1-φl2 class and Og-g-g- variations, and they are not reproduced correctly by the one-
and Og-g-x′+ are formed in the φl1-φl3 class. dimensional scheme. Whenever a g+ or x+ conformation occurs,
The influence of the oxygen on the conformers with three discrepancies are even enormous. The two-dimensional ap-
consecutive gauche standings weakens when they occur large proach, on the other hand, is quite accurate. The difference
distances from the oxygen (e.g., in the dihedral angles φl2- between the exact and the two-dimensional prediction only
φl4). An n-alkane-like behavior makes its appearance in a more exceeds 1 kJ/mol for the Otg-x-g+ and Otg-g-x+ conformers
pronounced way. According to the Tasi rules,5 one could expect of MPeE. For all other conformers, the discrepancy is limited
six conformers: g-g-g-, x+g-g-, g+x-g-, x-g+x-, g-x-g+, and to 0.5 kJ/mol. The adequacy of the two-dimensional approxima-
g-g-x+. However, this pattern is not entirely found according tion in describing fully coupled three-dimensional features in
to the constraints reported in the previous paragraph, restricting n-alkanes has already been reported in ref 3. Energy estimates
the first two rotations (φl2 and φl3) to reside in g-g-/g+g+ or based on a one-dimensional scheme (∆E1D-est) are manifestly
x′+g-/x′-g+ double gauche conformations. This additional inadequate.
constraint reduces the total number of conformations of this In summary, we have found a set of rules for deducing all
class to five, as given in Table 8. conformers in ethers. These are based on the possible occurrence
These findings enable us to propose an adjusted version of of double gauche sequences in these compounds. Starting from
Tasi’s rules which can be applied on ethers. Starting from the the general n-alkane rules of Tasi et al.,5 one can eliminate
original rules suitable for n-alkanes, one can impose some several conformers on the basis of these gg combinations. In
additional constraints in the sense that when a particular double addition, a two-dimensional scheme has been proposed which
gauche sequence is not allowed in a conformer, it remains is adequate for describing all possible conformers and their
excluded in the structure of all other conformers with multiple relative energies solely based on information for conformers
gauche conformations. To illustrate with an example, from Table with single and double gauche standings.
7 it follows that some g-g+ sequences are not occurring. In the 4.4. Sulfides. In view of the evident similarity between the
formation of conformers with three or more gauche standings, two types of molecules, all sulfides are discussed in comparison
we can a priori eliminate all combinations having this particular with the ether properties. More specifically, methyl ethyl sulfide
g-g+ sequence. (MES), methyl propyl sulfide (MPS), methyl butyl sulfide
Since the occurrence of a triple gauche conformer is mainly (MBS), methyl pentyl sulfide (MPeS), diethyl sulfide (DES),
determined by the rules governing two consecutive gauche ethyl propyl sulfide (EPS), ethyl butyl sulfide (EBS), and
conformations, it is reasonable to assume that its energy could dipropyl sulfide (DPS) are considered. Only a selection of the
be better approximated by including energy effects of all gg results is presented in the paper, but all other results are available
conformations. In this two-dimensional approach, the relative as Supporting Information (Tables 4 and 5).
Rules for Generating Conformers in n-Alkanes J. Phys. Chem. A, Vol. 109, No. 42, 2005 9625

The analogy between the conformers with a single gauche TABLE 9: Overview of Alterations of Tasi’s Rule for
of both systems can be examined in Table 6. The energies of Alkane Conformers in Ethers and Sulfidesa
sulfide conformers with one gauche in either φl1 or φs1 is very Double Gauche Conformers
close to the all-trans reference energy. In this respect, sulfides
φs1φl1 φl1φl2 φl2φl3 φl3φl4
clearly differ from ethers, in which the φl2 or φs2 single gauche
conformers closely match the all-trans energy. The φl2 rotations Tasi ethers
g-g- x-Ox- Og-g- Otg-g- Ottg-g-
in sulfides show the opposite behavior: the energy differences g-x+ (x-Ox+) Otg-x′+ Ottg-x+
amount to 2.7 kJ/mol, with dihedral angles of 66°. A complete x-g+ Ottx-g+
accordance between ethers and sulfides is only found for the Tasi sulfides
φl3 and φl4 gauche conformers, for which the energies and g-g- g-Sg- Sg-g- Stg-g- Sttg-g-
dihedral angles actually converged to typical alkane values. g-x+ g-Sx+ Stx′-x′+ Sttg-x+
x-g+ x-Sg+ Sx-g+ Sttx-g+
The discussion of conformers with two gauche dihedrals is
limited to EBS (Table 7), since the other sulfides yield similar Triple Gauche Conformers
results. Some striking differences with ethers are observed. It φs1φl1φl2 φl1φl2φl3 φl2φl3φl4
appears that several sequences of gauche standings with the
Tasi ethers
opposite orientation are not forbidden. For the φs1-φl1 interac- g-g-g- x-Ox-g- Og-g-g- Otg-g-g-
tion, there is even a doubling of conformers (x-Sg+tt and x+g-g- Otx′+g-g-
g-Sx+tt). This is analogous with the alkane situation, but here x-g+x- Otx′-g+x-
the dihedrals are substantially more distorted with angles of up g-g-x+ Og-g-x′+ Otg-g-x+
to 97°. These conformers have 3 kJ/mol of additional energy g-x-g+ Otg-x-g+
Tasi sulfides
as compared to the g-Sg-tt conformer. g-g-g- g-Sg-g- Sg-g-g- Stg-g-g-
There is only one conformer with opposite gauche orientations g+x-g- g+Sx-g- Stx′+x′-g-
for the φl1-φl2 and φl2-φl3 interactions: tSx-g+t and tStx′-x′+, x+g-g- (x+Sg-g-) Sx+g-g-
respectively. As from the φl3-φl4 interaction, the conformers x-g+x- Sx-g+g- Stx-g+x-
have full alkane-like features. This is illustrated for MPeS in g-g-x+ Sg-g-x+ Stg-g-x+
g-x-g+ g-Sx-g+ Sg-x-g+ Stg-x-g+
the Supporting Information (Table 4). Stg-x′-x′+
The one-dimensional energy estimates ∆E1D-est AB are only a The conformers given in parentheses occur for the smallest
adequate for conformers with two consecutive gauche standings
molecules only, and are of no importance for the general behavior of
of equal orientation. In contrast, the ∆E1D-est
AB values consider- (longer) ethers and sulfides.
ably underestimate the energy of the conformers with opposite
gauche orientations, up to 6 kJ/mol for tStx′-x′+. This partial n-alkanes deduced by Tasi et al.5 for these systems. Essentially,
success and partial failure is also observed for ethers, for this was accomplished by identifying that part of the molecule
alcohols and thiols, and for n-alkanes.3 not obeying Tasi’s law, and by analyzing all possible conformers
For the study of three consecutive gauche standings (Table in this part of the molecule.
8), we also restrict the discussion to EBS. The number of For alcohols and thiols, it was found that the HXCH2CH2CH2
conformers is definitely higher than in ethers, but still less than (X ) O or S) top is the part distinct from n-alkanes, while for
that predicted by Tasi’s alkane rules. Furthermore, it is not ethers and sulfides, third-order rotations from the heteroelement
possible to predict the occurrence of triple gauche conformers (φs3 f φl3) have to be taken into consideration to sufficiently
on the basis of the double gauche conformers. This also applies account for the effects of the oxygen or sulfur. The conforma-
for the (φl2,φl3,φl4) conformers of MPeS (Table 5 of the tional structure and pattern of the hetero region differ in the
Supporting Information). four types of molecules.
By confronting the relative energies for these conformers with The identification of this region of hetero influence (φs3 f
the predictions obtained in the one- and two-dimensional φl3) enables us to make some assumptions for carbon chains
approaches, we confirmed that the ∆E1D-est AB energies do not with multiple heteroelements. It is clear that when these
describe the correct features. The ∆E2D-est
ABC values on the other heteroatoms are separated by fewer than six bonds, both regions
hand are very satisfactory, describing both stabilization effects of influence are likely to interact and change the relative energy
(g-g-g-) and additional energies for conformers with g-g+ and geometry of the conformations in this area. When the
sequences. heteroelements are separated by at least six bonds, a reduced
mutual influence can be expected, although other intramolecular
5. Overview of Conformational Rules effects (e.g., hydrogen bonding, anomeric resonance) cannot be
excluded. This will no doubt affect the predicted conformations.
The revised Tasi rules (up to triple gauche) for ethers and
sulfides are presented in Table 9. It is obvious that the region Only thiols exhibit a distinct global minimum [HSg(tttt)]. All
exposed to the specific influence of the heteroelement is φs2 f other conformers are at least 2 kJ/mol less bound. For the three
φl2. In other words, all double or triple consecutive gauche other types of molecules, no strict rules can be proposed for
conformers involving one of these internal rotations do not obey the ground-state configuration. Many conformers are competing
Tasi’s alkane rule. within an energy interval of 1 kJ/mol. An accurate description
of molecular properties, even at low temperatures, requires a
The specific conformers of primary alcohols and thiols not
complete knowledge of all existing conformers. It is thus
obeying Tasi’s law are presented in Tables 3 and 4.
important to use a model that generates all low-energy conform-
ers.
6. Summary
While for primary alcohols and thiols it is possible to
In this work, we performed a conformational analysis of reproduce all conformers specific to the functional group (14
alcohols, thiols, ethers, and sulfides. Our main goal was to and 15, respectively), this becomes more cumbersome for ethers
modify the general rules for the occurrence of conformers in and sulfides, because the heteroelement now affects two alkyl
9626 J. Phys. Chem. A, Vol. 109, No. 42, 2005 Vansteenkiste et al.

side chains. For this reason, we have focused on conformers (16) (a) Becke, A. D. Phys. ReV. B 1988, 38, 3098. (b) Perdew, J. P.;
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Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A.
with the reference conformer.36,37 Using the energy scheme D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi,
introduced in this work, one is able to determine the importance M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.;
of every conformer (at a given temperature) without the need Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick,
D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.;
of explicit calculations. Ortiz, J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, B.; Liashenko, A.; Piskorz,
Our rules may thus serve as a fast method for selecting those P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-
conformers with associated energies below a given energy Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe,
M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.;
threshold, and therefore with a significant contribution to the Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian
desired property. 98, revision A.7; Gaussian, Inc.: Pittsburgh, PA, 1998.
(24) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb,
Acknowledgment. This work is supported by the Fund for M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K.
Scientific Research-Flanders (FWO) and the Research Board N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.;
Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.;
of Ghent University. Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.;
Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li,
Supporting Information Available: Relative energies of X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.;
Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.;
the five conformers of 1-propanol (Table 1), absolute dihedral Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.;
angles of the different conformers in primary alcohols (Table Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels,
2), relative energies of selected alkane-like conformers of A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.;
primary thiols (Table 3), relative energies of the double gauche Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.;
Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz,
conformers of sulfides (Table 4), and relative energies of the P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.;
triple gauche conformers of sulfides (Table 5). This material is Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson,
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