Spin-orbit Effects on the Structure of Haloiodomethane Cations CH_{2}XI^{+} (X

Bulletin of the Korean Chemical Society.
2014.
Mar,
35(3):
775-782

- Received : August 23, 2013
- Accepted : September 09, 2013
- Published : March 20, 2014

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The importance of including spin-orbit interactions for the correct description of structures and vibrational frequencies of haloiodomethanes is demonstrated by density functional theory calculations with spin-orbit relativistic effective core potentials (SO-DFT). The vibrational frequencies and the molecular geometries obtained by SO-DFT calculations do not match with the experimental results as well as for other cations without significant relativistic effects. In this sense, the present data can be considered as a guideline in the development of the relativistic quantum chemical methods. The influence of spin-orbit effects on the bending frequency of the cation could well be recognized by comparing the experimental and calculated results for CH
_{2}
BrI and CH
_{2}
ClI cations. Spin-orbit effects on the geometries and vibrational frequencies of CH
_{2}
XI (X=F, Cl, Br, and I) neutral are negligible except that C-I bond lengths of haloiodomethane neutral is slightly increased by the inclusion of spin-orbit effects. The
^{2}
A' and
^{2}
A'' states were found in the cations of haloiodomethanes and mix due to the spin-orbit interactions and generate two
^{2}
E
_{1/2}
fine-structure states. The geometries of CH
_{2}
XI
^{+}
(X=F and Cl) from SO-DFT calculations are roughly in the middle of two cation geometries from DFT calculations since two cation states of CH2XI (X=F and Cl) from DFT calculations are energetically close enough to mix two cation states. The geometries of CH
_{2}
XI+ (X=Br and I) from SO-DFT calculations are close to that of the most stable cation from DFT calculations since two cation states of CH
_{2}
XI (X=Br and I) from DFT calculations are energetically well separated near the fine-structure state minimum.
^{-}
3
and the spinorbit interaction is present in the relativistic formalism based upon Dirac operator for the electron. Spin-orbit and other relativistic effects required for the accurate description of valence states of molecules containing heavy elements can be represented as two-component relativistic effective core potentials (RECPs) derived from Dirac-Coulomb Hamiltonian based all-electron calculations of atoms.
4
Scalar relativistic effects are routinely included in electronic-structure calculations through the use of RECPs, but spin–orbit interactions are usually omitted when deriving optimized structures partly because of the assumption that their influence on the molecular structures is negligible and partly due to computational difficulties.
5
^{,}
6
Even when spin–orbit terms are available in RECPs, the usual treatment involves perturbational inclusion of these terms after the variational determination of orbitals and structures. Quantum chemical calculations employing RECPs with spin–orbit operators from the beginning of
ab initio
calculations have been available.
7
^{,}
8
Spin– orbit density functional theory (SO-DFT) method available in NWCHEM is particularly useful for the present purpose of demonstrating spin–orbit effects on geometries since the structures can be optimized with both spin–orbit interactions and electron correlations included.
9
^{,}
10
Relativistic effects on geometries of molecules containing heavy elements can be comparable or larger than electron correlation effects and make an unexpected shape to be a local minimum. We found this influence of spin-orbit interactions on the geometry for polyhalomethanes CH
_{2}
ClI
^{+}
and CH
_{2}
BrI
^{+}
cations in collaborations with the group of Prof. M. S. Kim.
11
^{-}
13
Polyhalomethanes have been of considerable interest in relation to ozone depletion in the atmosphere.
14
^{-}
16
The photochemistry of iodine containing polyhalomethanes such as CH
_{2}
ClI, CH
_{2}
BrI, and CH
_{2}
I
_{2}
have been actively investigated in this context for the role in the ozone depletion in the troposphere,
15
^{,}
17
^{,}
18
and also from the point of view of fundamental science for the importance of these molecules as prototypes of the reaction control
via
electronic state selection.
19
^{-}
21
Another important aspect in the fundamental study of these iodine containing molecules is the extent of the influence of relativistic effects on their structures and molecular properties.
11
^{,}
12
A conventional approach to handle this effect in the electronic structure calculation is to adopt RECPs for heavy elements. Spin-orbit interaction is usually omitted as noted above. The same approach is generally adopted to analyze the results from the photoelectron spectroscopy (PES) which provides low resolution spectroscopic data for cations.
22
^{,}
23
Zero kinetic energy (ZEKE) photoelectron spectroscopy
24
^{,}
25
and mass-analyzed threshold ionization (MATI) spectroscopy
26
are offspring of PES and provide much higher resolution spectroscopic data for cations. The vibrational spectra of the halomethane cations have been recorded using the MATI spectrometry.
11
^{-}
13
SO-DFT calculations for spectroscopic constants of mixed dihalomethanes have been performed using shape-consistent RECPs with effective one-electron spin-orbit operator to confirm and improve the phenomenological assignments.
In order to generalize and understand interesting spin-orbit effects obtained for CH
_{2}
ClI
^{+}
and CH
_{2}
BrI
^{+}
, we extend the study to include CH
_{2}
FI
^{+}
and CH
_{2}
I
_{2}
^{+}
. The vibrational frequencies of CH
_{2}
XI (X=F, Cl, Br, and I) neutral and cation were obtained from SO-DFT calculations. The shapes and energy levels of molecular orbitals from DFT calculations and the energy levels of molecular spinors from SO-DFT calculations were analyzed to reveal the origin of characteristic spin-orbit effects on the X-C-I bond angle.
et al.
,
27
where |
ljm
〉
〈ljm
| represents a two-component projection operator. Molecular spinors which are obtained as oneelectron wave functions of the Hamiltonian containing the above RECP have two components. The RECP, U
^{REP}
which is referred to SOREP here can be expressed as the sum of the scalar relativistic effective core potential (AREP), U
^{AREP}
, and the effective one-electron spin-orbit operator,
28
U
^{SO}
, as
Values calculated with AREP include scalar relativistic effects, and those with SOREP contain spin-orbit effects as well as scalar relativistic effects. The spin-orbit effects (Δ
_{SO}
) are defined as the difference between AREP and SOREP values calculated with the same basis set at a given level of theory.
SO-DFT calculations were done for the CH
_{2}
XI (X=F, Cl, Br, and I) neutral and cation in the ground electronic state with the B3LYP
29
(Becke's three parameter hybrid functional
30
with the Lee-Yang-Parr correlation functional
31
) functional using NWCHEM.
9
10
RECPs with the effective spin-orbit potentials and the basis sets for the valence shell reported by Christiansen and coworkers
32
33
were used for halogen atoms. To this basis set of F, Cl, Br, and I, the diffuse and polarization functions reported by Lee
et al.
5
were added to make halogen basis sets consistent with the large basis sets used for other atoms as shown in
Table 1
. AREP and SOREP calculations were performed to observe the magnitude of spin-orbit effects. The step size in the calculation of the numerical Hessian was optimized to produce reliable vibrational frequencies. Equilibrium geometries and vibrational frequencies of the neutral and the cation were calculated.
^{a}RECPs and basis sets used for halogen atoms are in Refs. 32 and 33 and spin-orbit terms in the same references were used when needed.
Six sets of DFT calculations were performed for CH
_{2}
ClI to test the effects of the type of functionals. The applied hybrid functionals were B3LYP,
29
ACM
30
(Becke’s adiabatic connection method, also known as B3PW91) and PBE0
34
35
(Perdew-Burke-Ernzerhof parameter-free functional) functionals. Additional DFT calculations use local density approximation (LDA), generalized gradient approximation (GGA), and hybrid meta-GGA (HMGGA) of the exchange-correlation functionals to gauge the reliability of the hybrid functionals. The applied LDA and GGA functionals are SVWN5 (Slater exchange
36
and Vosko-Wilk-Nusair correlation functional (VWN)
37
), BP86 (Becke exchange
38
and Perdew correlation functional
39
), respectively. The applied HMGGA functionals is M05
40
(Minnesota 2005). It is noted that RECPs used here are all generated using relativistic HF results and may introduce some inconsistency when used with DFT methods. We assume this error to be small enough at least for the purposes of the present study.
Test Calculations for CH_{2}ClI.
DFT calculations with several functionals were performed for CH
_{2}
ClI and optimized geometrical parameters are listed in
Table 2
. There are the functional dependencies on the bond lengths of CH
_{2}
ClI neutral, while that on the bond angles are small as shown in
Table 2
. Spin-orbit effects on the geometries of CH
_{2}
ClI neutral are negligible except on the C-I bond lengths for which spinorbit effects slightly increase the bond length. The most pronounced discrepancy from experimental geometrical parameters is the C-I bond length. All calculated C-I bond lengths of CH
_{2}
ClI from DFT and SO-DFT calculations are overestimated compared to the experimental ones. The C-I bond lengths of CH
_{2}
ClI from HF and SO-HF calculations are closer to the experimental one. The C-I bond lengths of CH
_{2}
ClI from DFT calculations have rather small variation with the class of the functional employed among LDA, GGA and HGGA. LDA yields shortest one followed by HGGA and then GGA. Roughly speaking, the C-I bond lengths of CH
_{2}
ClI from DFT calculations with functionals including HF exchange contribution, which are hybrid functionals, are indirectly proportional to the amount of the HF exchange contribution to the functionals. The C-I bond lengths of CH
_{2}
ClI from DFT calculations with functionals including HF exchange contribution are 2.181 (B3LYP with 20% HF exchange), 2.163 (ACM or B3PW91 with 20% HF exchange), 2.154 (PBE0 with 25% HF exchange), 2.152 (M05 with 28% HF exchange), and 2.151 (BHLYP with 50% HF exchange). The hybrid functional with the larger HF exchange results in the shorter C-I bond length and closer to experimental one. The vibrational frequencies of CH
_{2}
ClI neutral from DFT calculations with hybrid functional are overestimated compared to experimental ones. Since HF results for energies and vibrational frequencies are not reliable, we may select DFT and hybrid functionals among DFT as the method of choice for chloroiodomethane.
^{a}The set 1 basis sets and RECPs in Table 1 were used. ^{b}Microwave spectroscopic data from Ref.42
^{a}The set 1 basis sets and RECPs in Table 1 were used.
Two stationary states,
^{2}
A' and
^{2}
A'', of the chloroiodomethane cation corresponding to removal of HOMO
_{‒1}
a'
and HOMO
a''
, respectively, from the neutral molecule can be obtained in AREP-HF and AREP-DFT calculations. The optimized structures of the two cation states indicate that structural change from the neural one is larger for the
^{2}
A' state than for the
^{2}
A'' state, It appears that antibonding interaction for the
a'
orbital is larger than that in the
a''
orbital as can be seen in
Figure 1
. Reflecting this larger geometry changes, the most stable cation of CH
_{2}
ClI is the
^{2}
A' state generated by removal of an electron from the second highest occupied
a'
orbital (
Fig. 1
). Qualtitative changes from neutral to the two cation states in
Table 3
are essentially similar for all methods. One exception is the C-I bond length. HF gives longer bond lengths for cation states while LDA and GGA produce shorter ones for the cation states. It appears that electron correlations shorten the C-I bond lengths, which is also observed in all-electron calculations.
41
It is noted that this trend is opposite to that in the neutral. The
^{2}
A' and
^{2}
A'' states mix due to the spin-orbit interactions and generate two
^{2}
E
_{1/2}
fine-structure states. The energy differences of two cation states from AREP calculations for CH
_{2}
ClI
^{+}
is about 1200 cm
^{‒1}
. Energetically close two states of chloroiodomethane cation mix substantially to generate the fine-structure states with geometries somewhere between two AREP states. The geometries of CH
_{2}
ClI from SO-DFT calculations are roughly in the middle of two cation geometries especially in terms of the Cl-C-I bond angle. In this regard, HF and all DFT functional considered afford the same trend. This has been the subject of several reports. We try to observe the general pattern of this behavior by considering other members of CH
_{2}
XI
^{+}
, The performance of HF and various DFT methods for the cation is similar to that for the neutral case and we proceed to use B3LYP with AREP and SOREP for other members of CH
_{2}
XI.
Shapes and energy levels (energy levels) of molecular orbitals (molecular spinors) from the B3LYP (SO-B3LYP) calculations for CH_{2}XI (X=F, Cl, Br, and I). For each molecule orbital energy levels are on the left column and molecular spinor energy levels are open the right. Each dotted line connecting an orbital with a spinor imply spin-orbit coupling.
Spin-orbit Effects on the Vibrational Frequencies of Haloiodomethane Cations (CH_{2}XI^{+} (X=F, Cl, Br, and I)).
Spin-orbit effects on the geometries and vibrational frequencies of CH
_{2}
XI (X=F, Cl, Br, and I) neutral are negligible as shown in
Tables 4
and
5
. The C-I bond length of haloiodomethane neutral is slightly increased by the inclusion of spin-orbit effects. Calculations incorporating spin-orbit terms still need to achieve more accurate theoretical results. The calculated C-I bond lengths of CH
_{2}
ClI and CH
_{2}
I
_{2}
are overestimated in comparison to the available experimental ones.
42
43
The calculated C-I bond lengths of CH
_{2}
BrI and CH
_{2}
I
_{2}
are longer than the available CASPT2 results.
44
45
DFT calculations with the B3LYP functional using RECPs by Christiansen
et al.
32
33
seem to overestimate the C-I bond lengths, but the degree of overestimate is not so large as to affect the reliability of the present study. The C-X bond lengths of CH
_{2}
XI (X=F, Cl, Br, and I) increase on descending the halogen group in the periodic table, as expected from the increasing size of halogen atoms. The C-I bond lengths of CH
_{2}
XI (X=F, Cl, Br, and I) decrease on descending the halogen group in the periodic table. The X-C-I bond angle of CH
_{2}
XI (X=F, Cl, Br, and I) increases on descending the halogen group in the periodic table probably due to the increasing steric repulsion between X and I. In order to reduce the steric repulsion between X and I, the shorter C-X bond length induces the longer C-I bond length. The X-C-I bond angle of CH
_{2}
I
_{2}
is also larger than that of CH
_{2}
FI indicating that the steric repulsion between Two I atoms is larger than that between F and I atoms.
The shapes and energy levels of molecular orbitals and energy levels of molecular spinors of CH
_{2}
XI (X=F, Cl, Br, and I) neutral are shown in
Figure 1
. For CH
_{2}
XI (X=F and Cl), HOMO and HOMO
_{−1}
have
a''
and
a'
symmetries, respectively. For CH
_{2}
BrI and CH
_{2}
I
_{2}
, HOMO and HOMO
_{−1}
have
a'
and
a''
symmetries, respectively. The
a'
and
a''
correspond largely to the iodine 5
p
nonbonding orbtials, parallel n(I5
p
_{||}
) and perpendicular n(I5
p
_{⊥}
), respectively, to the molecular plane as shown in
Figure 1
. The a' orbitals are two inplane nonbonding orbitals, n(I5
p
_{||}
) and n(X
np
_{||}
). The in-plane nonbonding orbitals of two halogens have small antibonding interactions with each other The antibonding characteristics of
a'
orbitals for CH
_{2}
XI (X=F, Cl, Br, and I) increase on descending the periodic table. Thus the energy levels of molecular orbitals increase for the lower members of the halogen group in the periodic table. The
a''
orbitals have the perpendicular nonbonding orbital, n(I5
p
_{⊥}
). The energy levels of molecular orbitals are all similar in CH
_{2}
XI (X=F, Cl, Br, and I). As a result, the destabilization of a' orbitals induces the symmetry alternation of HOMO and HOMO
_{−1}
in CH
_{2}
XI (X=Br and I) compared with CH
_{2}
XI (X=F and Cl). Thus the gap in energy levels of HOMO and HOMO
_{−1}
in CH
_{2}
ClI (299 cm
^{−1}
) and CH2BrI (379 cm
^{−1}
) are closer than that in CH
_{2}
FI (1302 cm
^{−1}
) and CH
_{2}
I
_{2}
(1813 cm
^{−1}
). The HOMO and HOMO
_{−1}
levels in DFT calculations shift due to spin-orbit interactions and generate highest occupied molecular spinor (HOMS) and HOMS
_{−1}
in SO-DFT calculations. Actually all energy levels are affected by spin-orbit interactions. The closer the energy levels in DFT calculations, the larger the spin-orbit splitting in SO-DFT calculations. The splitting of HOMS and HOMS
_{−1}
energy levels due to spin-orbit effects are 4751 cm
^{−1}
for CH
_{2}
FI, 4448 cm
^{−1}
for CH
_{2}
ClI, 3956 cm
^{−1}
for CH
_{2}
BrI, and 5402 cm
^{−1}
for CH
_{2}
I
_{2}
.
^{a}The set 1 basis sets and RECPs in Table 1 were used. ^{b} Microwave spectroscopic data from Ref.42 ^{c} B3LYP/Sadlej-PVTZ calculations from Ref.46 ^{d} CASSCF/ANO-RCC calculations from Ref.44 ^{e} CASPT2/ANO-RCC calculations from Ref.44 ^{f} BLYP calculations from Ref.47 ^{g} MP2 calculations from Ref.48 ^{h} QCISD calculations from Ref.49 ^{i} CASPT2L1 calculations from Ref.45 ^{j} Ref.43
^{a} The set 1 basis sets and RECPs in Table 1 were used. ^{b} Mulliken notation. ^{c} Raman spectroscopic data from Ref.50 ^{d} Raman spectroscopic data from Ref.51 ^{e} B3LYP/Sadlej-PVTZ data from Ref.46 ^{f} CASSCF/ANO-RCC calculations from Ref.44 ^{g} CASPT2/ANO-RCC calculations from Ref.44 ^{h} Raman spectroscopic data from Ref.19 ^{i} Raman spectroscopic data from Ref.52
Similar analysis is possible for lower lying halogen orbitals. For CH
_{2}
XI (X=F, Cl, and Br), HOMO
_{−2}
and HOMO
_{−3}
have
a'
and
a''
symmetries, respectively. For CH
_{2}
I
_{2}
, HOMO
_{−2}
and HOMO
_{−3}
have
a''
and
a'
symmetries, respectively. The
a'
and
a''
orbitals correspond to the antibonding combination of mainly nobonding orbitals parallel and perpendicular to the molecular plane, respectively, as shown in
Figure 1
. The
a'
orbitals have two in-plane orbitals a(I5
p
_{||}
) and a(X
np
_{||}
) in antibonding combination. The antibonding characters of
a'
orbitals for CH
_{2}
XI (X=F, Cl, Br, and I) increase on descending the halogen group in the periodic table in line with increase in the energy levels of molecular orbitals. The
a''
orbitals comprise the perpendicular nonbonding orbital, n(I5
p
_{⊥}
), n(X
np
_{||}
) and small contributions from the CH
_{2}
fragment. The perpendicular nonbonding orbitals of two halogens have slight antibonding interactions with each other. The antibonding characters of
a''
orbitals for CH
2
XI (X=F, Cl, Br, and I) also increase on descending the halogen group in the periodic table, and the energy levels of molecular orbitals rise on descending the halogen group in the periodic table. The extent of the destabilization of
a''
orbitals is faster than that of
a'
orbitals, which results in the symmetry alternation of HOMO
_{−2}
and HOMO
_{−3}
in CH
_{2}
I
_{2}
in comparison to CH
_{2}
XI (X=F, Cl, and Br). The destabilization of HOMO
_{−2}
and HOMO
_{−3}
is faster than that of HOMO and HOMO
_{−1}
. For CH
_{2}
I
_{2}
, the energy levels of HOMO, HOMO
_{−1}
, HOMO
_{−2}
, and HOMO
_{−3}
are quite close.
The spin-orbit splitting of the HOMO
_{−2}
and HOMO
_{−3}
levels to the HOMS
_{−2}
and HOMS
_{−3}
levels strongly depends on the X halogen atom. The energy levels of HOMO
_{−2}
and HOMO
_{−3}
for CH
_{2}
XI (X=F and Cl) are similar to those of HOMS
_{−2}
and HOMS
_{−3}
, reflecting small spin-orbit splittings of F and Cl. The HOMO
_{−2}
and HOMO
_{−3}
levels for CH
_{2}
XI (X=Br and I) in DFT calculations split further due to the spin-orbit interactions and generate more separated HOMS
_{−2}
and HOMS
_{−3}
in SO-DFT calculations. The closer the energy levels in DFT calculations, the larger the spin-orbit splitting in SO-DFT calculations. For CH
_{2}
I
_{2}
, the spin-orbit splitting between the HOMO and HOMO
_{−1}
levels decrease the HOMO
_{−1}
level and that of the HOMO
_{−2}
and HOMO
_{−3}
levels increase the HOMO
_{−2}
level. Thus, the HOMS
_{−1}
level is mainly from spin-orbit splitting of HOMO
_{−2}
and the HOMS
_{-2}
level is mainly from spin-orbit splitting of HOMO
_{−1}
since the energy levels of HOMO, HOMO
_{−1}
, HOMO
_{−2}
, and HOMO
_{−3}
are close as shown in
Figure 1
. The above interpretation of the spin-orbit splitting is an attempt to identify major factors. Since all molecular orbitals and also molecular spinors are mixtures of X and I atomic orbitals, additional orbital interactions play a role in determining accurate positions of energy levels.
Two stationary states,
^{2}
A' and
^{2}
A'', of haloiodomethane cations were found from AREP calculations, and the geometries and vibrational frequencies of CH
_{2}
XI
^{+}
molecules are summarized in
Tables 6
and
7
. The stable cation of haloiodomethane except CH
_{2}
ClI from AREP calculations is generated by the removal of an electron from the HOMO. The most stable cation of CH
_{2}
FI is the
^{2}
A'' state generated by the removal of an electron from the highest occupied
a''
orbital. The most stable cation of CH
_{2}
XI (X=Br and I) is the
_{2}
A' state generated by the removal of an electron from the highest occupied
a'
orbital while the most stable cation of CH
_{2}
ClI is the
^{2}
A' state generated by the removal of an electron from the second highest occupied
a'
orbital. The
^{2}
A' state has much smaller X-C-I angles than the neutral molecule in all CH
_{2}
XI, implying that the shape of the cation in this state is somewhat different from the neural molecule. On the contrary, the
^{2}
A' state of the cation has the X-C-I angle similar to the neural molecule. Vibrational frequencies of the cation states do not differ too much for the X-C-I bending mode (ν
_{6}
in
Tables 5
and
7
) except for CH
_{2}
FI. The two
^{2}
A' and
^{2}
A'' states mix due to the spin-orbit interactions and generate two
^{2}
E
_{1/2}
states. The energy differences of two cation states from AREP calculations for CH
_{2}
FI, CH
_{2}
ClI, CH
_{2}
BrI, and CH
_{2}
I
_{2}
are 834, 1225, 2768, and 3584 cm
^{−1}
in
Table 5
. Energetically closer two states of cations of haloiodomethanes mix more substantially than energetically less close two states of cations. The geometries of CH
_{2}
XI
^{+}
(X=F and Cl) from SO-DFT calculations are roughly in the middle of two cation geometries from DFT calculations since two cation states of CH
_{2}
XI (X=F and Cl) from DFT calculations are energetically close enough to mix two cation states. In contrast, the geometries of CH
_{2}
XI (X=Br and I) from SODFT calculations are close to those of more stable cations from DFT calculations since two cation states of CH
_{2}
XI (X=Br and I) from DFT calculations are energetically not so close enough to produce well mixed fine-structure states. In this sense, large spin-orbit induced shape change is predicted for CH
_{2}
FI and CH
_{2}
ClI, but not for CH
_{2}
BrI and CH
_{2}
I
_{2}
. One confirmation of this is the X-C-I bending mode in
Table 7
since this ν6 bending mode reflects bonding property of the X-C-I bond angle. Energetics of spin-orbit effects will be important in analyzing PES data, but this is not attempted here.
^{a} The set 1 basis sets and RECPs in Table 1 were used. ^{b} B3LYP/Sadlej-PVTZ data from Ref.46
^{a} The set 1 basis sets and RECPs in Table 1 were used. ^{b} Mulliken notation. ^{c} MATI spectroscopic data from Ref.11 12 ^{d} MATI spectroscopic data from Ref.13
_{2}
XI (X=F, Cl, Br, and I) neutral are negligible except that C-I bond lengths of haloiodomethane neutral is slightly increased by the inclusion of spin-orbit effects. The
^{2}
A' and
^{2}
A'' states were found in the cations of haloiodomethanes and mix due to the spin-orbit interactions and generate two
^{2}
E
_{1/2}
fine-structure states. The energy differences of two cation states from AREP calculations for CH
_{2}
FI
^{+}
, CH
_{2}
ClI
^{+}
, CH
_{2}
BrI
^{+}
, and CH
_{2}
I
_{2}
^{+}
are 834, 1225, 2768, and 3584 cm
^{‒1}
. The geometries of CH
_{2}
XI
^{+}
(X=F and Cl) from SO-DFT calculations are roughly in the middle of two cation geometries from DFT calculations since two cation states of CH
_{2}
XI (X=F and Cl) from DFT calculations are energetically close enough to mix two cation states. The geometries of CH
_{2}
XI
^{+}
(X=Br and I) from SO-DFT calculations are close to that of most stable cation from DFT calculations since two cation states of CH
_{2}
XI (X=Br and I) from DFT calculations are energetically not close enough near the fine-structure state minimum to extensively mix two cation states.

Introduction

Quantum chemical calculations could provide results comparable to experimental measurements in many instances, but still need improvement in the accuracy and reliability. One such direction is the inclusion of spin-orbit interactions in Hamiltonian. The importance of relativity for the description of heavy elements is well recognized,
1
Computational Details

Optimized molecular geometries of haloiodomethane CH2XI neutral and cation (X=F, Cl, Br, and I) were calculated at the DFT level of theory employing RECPs including spin-orbit terms. The RECP employed for the present calculations is expressed by the following form within the framework originated from Lee
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Basis sets and RECPs used in the SO-DFT calculations with the B3LYP functionala

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Results and Discussion

Geometries of CH2ClI neutral in the ground electronic state without (w/o) and with (w/) spin-orbit effectsa

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Geometries of CH2ClI cation in the ground electronic state without (w/o) and with (w/) spin-orbit effectsa

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Geometries of CH2XI (X = F, Cl, Br, and I) neutral in the ground electronic state calculated without (w/o) and with (w/) spin-orbit interactionsa

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Vibrational frequencies (in cm‒1) of CH2XI (X = F, Cl, Br, and I) neutral in the ground electronic state calculated without (w/o) and with (w/) spin-orbit interactionsa

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Geometries of CH2XI (X = F, Cl, Br, and I) cation in the ground electronic state without (w/o) and with (w/) spin-orbit effectsa

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Vibrational frequencies (in cm‒1) of CH2XI (X = F, Cl, Br, and I) cation in the ground electronic state calculated without (w/o) and with (w/) spin-orbit effectsa

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Conclusion

The importance of including spin-orbit interactions for the correct description of structures and vibrational frequencies of haloiodomethanes is demonstrated by DFT calculations with spin-orbit relativistic effective core potentials. The vibrational frequencies and the molecular geometries obtained by SO-DFT calculations do not match with the experimental results as well as for other cations without significant relativistic effects. In this sense, the present data can be considered as a guideline in the development of the relativistic quantum chemical methods. The influence of spin-orbit effects on the bending frequency of the cation could be recognized by comparing the experimental and calculated results.
Spin-orbit effects on the geometries and vibrational frequencies of CH
Acknowledgements

This paper is dedicated to Professor Myung Soo Kim on the occasion of his honourable retirement. Authors also thank Professor Myung Soo Kim and Dr. M. Kim for the collaboration in the study of chloro- and bromo- iodomethanes, which initiated this work. The research is supported by grants (2007-0056095, 2012-R1A1A2000915) from National Research Foundation funded by Korea government. Computational resouces were partly provided by KISTI (KSC-2012-C2-81).

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Citing 'Spin-orbit Effects on the Structure of Haloiodomethane Cations CH_{2}XI^{+} (X
'

@article{ JCGMCS_2014_v35n3_775}
,title={Spin-orbit Effects on the Structure of Haloiodomethane Cations CH_{2}XI^{+} (X}
,volume={3}
, url={http://dx.doi.org/10.5012/bkcs.2014.35.3.775}, DOI={10.5012/bkcs.2014.35.3.775}
, number= {3}
, journal={Bulletin of the Korean Chemical Society}
, publisher={Korean Chemical Society}
, author={Kim, Hyoseok
and
Park, Young Choon
and
Lee, Yoon Sup}
, year={2014}
, month={Mar}