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On the intermolecular interactions ofisothiocyanic acid (HNCS) with disulfurmonoxide (SSO): a first principlesapproachEsmail Vessallya, Ali Mortezapourb & Moein Goodarzica Department of Science, Payame Noor University, P. O. Box19395–4697, Tehran, Iranb Department of Physics, University of Guilan, P. O. Box41335–19141, Rasht, Iranc Department of Chemistry, Institute for Advanced Studies in BasicSciences (IASBS), Zanjan, IranPublished online: 23 May 2014.

To cite this article: Esmail Vessally, Ali Mortezapour & Moein Goodarzi (2014) On the intermolecularinteractions of isothiocyanic acid (HNCS) with disulfur monoxide (SSO): a first principles approach,Journal of Sulfur Chemistry, 35:5, 484-492, DOI: 10.1080/17415993.2014.917376

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Journal of Sulfur Chemistry, 2014Vol. 35, No. 5, 484–492, http://dx.doi.org/10.1080/17415993.2014.917376

On the intermolecular interactions of isothiocyanic acid (HNCS)with disulfur monoxide (SSO): a first principles approach

Esmail Vessallya∗, Ali Mortezapourb and Moein Goodarzic∗

aDepartment of Science, Payame Noor University, P. O. Box 19395–4697, Tehran, Iran; bDepartment ofPhysics, University of Guilan, P. O. Box 41335–19141, Rasht, Iran; cDepartment of Chemistry, Institute forAdvanced Studies in Basic Sciences (IASBS), Zanjan, Iran

(Received 16 January 2014; accepted 18 April 2014 )

The geometrical structure and binding energy of all the possible heterodimers of isothiocyanic acid (HNCS)with disulfur monoxide (SSO) have been studied in the gas phase, theoretically. Nine minima (with noimaginary frequencies) are located on the singlet potential energy surface of the HNCS–SSO system at theMP2 level with binding energies (corrected with ZPE and BSSE) in the range 5.53–19.12 kJ/mol. Bader’squantum theory of atoms in molecules has been employed to elucidate the intermolecular interactioncharacteristics of the HNCS–SSO system. All intermolecular interactions in the HNCS–SSO system areweak interactions of non-covalent without any covalent characters.

Keywords: isothiocyanic acid; disulfur monoxide; intermolecular interaction; binding energy; AIM

1. Introduction

The isothiocyanic acid (HNCS) is a sulfur analog of the well-known isocyanic acid (HNCO).Many investigations in both of theoretical and experimental have been performed on the structure,

∗Corresponding author. Emails: Vessally@yahoo.com; Moein.Goodarzi20@gmail.comThis article makes reference to supplementary material available on the publisher’s website at http://dx.doi.org/10.1080/17415993.2014.917376.

© 2014 Taylor & Francis

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stability and photolytic behavior of HNCO and its structural isomers.[1–12] In contrast, HNCSand its isomers were less studied up to now. There are several papers on its IR,[13,14] microwave[15,16] and UV [17] spectra. Flash photolysis of HNCS was also reported.[18] Durig and Wertz[19] have performed detailed infrared investigation of HNCS and DNCS in gaseous and solidphases and in argon matrices. High resolution rotational–vibrational spectra of the acid have alsobeen studied.[20] Later on, theoretical [21] and the rotational spectrum of HNCS [22,23] haveconfirmed the structure of the HNCS as a quasi-linear molecule. Wierzejewska and Mielke [24]have reported near UV photolysis and the infrared matrix isolation studies of HNCS.[25]Also, theyhave carried out ab initio calculations on HNCS and its complexes with nitrogen and xenon.[25]The theoretical study of Bak et al. [21] shows that a stability of HNCS and its isomers should be inthe order of HNCS > HSCN > HSNC > HCNS. Durig et al. [26] have determined the structuralparameters and vibrational spectra of the HNCS molecule, theoretically. Very recently, Wang et al.[27] have investigated the mechanism of thermal decomposition of thiourea, theoretically. Theirresults show that the HNCS can be easily formed through thermal decomposition of thiourea.

One of the interesting molecules which is predicted to be the component of atmosphere of theJupiter’s moon Io [28,29] and the planet Venus [30] is the disulfur monoxide (SSO) molecule.Also, the SSO molecule is reported to be produced in the earth’s atmosphere by the photo-chemical oxidation reactions of hydrogen disulfide and hydrocarbon disulfide compounds. Thesereactions suggest that SSO would be an intermediate from the photochemical oxidation of disul-fides. Because of the small amount of production or interference of by-products, the most of thesereactions are not suitable for experimentally investigating the characteristics of SSO. A relativelyclean process is the reaction of oxygen atoms with OCS, producing SO and CO. The decay ofSO, in the absence of O2 has been studied at 298 K from 2 to 8 Torr using a tubular flow reactorcoupled to a mass spectrometer. According to this study the formation of SSO from gaseousSO is a stepwise process.[31] Therefore, the reaction of oxygen atoms with OCS is suitable toproduce the SSO molecule. The formation of SSO is also reported to occur from the gaseousreactions of SO in a sulfur-rich environment.[32] The structure of the SSO molecule has beenreported in many published research papers.[33–40] Experimentally, the structure of the SSOmolecule has been determined by rotational spectroscopy.[41–43] Theoretically, high-level abinitio calculations support the open-chain structure for the ground state of SSO,[32,44] whiledensity functional calculations predict that a cyclic ground state structure is more stable.[45] Thereaction paths of SSO with O2 have been investigated theoretically, where the molecules of SO2

and SO are the products of the SSO + O2 reaction.[46] This means that the SSO molecule affectsacid rain because the formed SO reacts with O2 to produce SO3.[46–48]

Since the latter species play an important role in the earth’s atmosphere, it is important toobtain atmospheric information regarding their behaviors. In the present work, we study theheterodimers containing intermolecular interactions of HNCS with the SSO molecule to providea detailed examination of the stability and property of the HNCS–SSO system.

2. Computational methods

Ab initio calculations are carried out using the Gaussian 03 programs.[49] The geometries ofHNCS and SSO monomers and all the heterodimers are fully optimized by employing the Moller–Plesset second-order perturbation (MP2) method [50] with Dunning’s correlation-consistent basisset, cc-pVDZ [51] on the singlet potential energy surface (PES). In order to compute accu-rate relative energies, single-point energy calculations at the MP2/aug-cc-pVTZ level have beencarried out on the optimized geometries at the MP2/cc-pVDZ computational level (MP2/aug-cc-pVTZ//MP2/cc-pVDZ). Note that the interaction energy (EI) was calculated as the differencebetween the total energy of the heterodimer and the sum of total energies of the HNCS and SSO

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monomers. The vibrational frequencies are calculated at the MP2/cc-pVDZ level of the theorybased on the optimized geometries to determine the nature of the stationary points according tothe number of negative eigenvalues of the Hessian matrix. The heterodimers possess no imaginaryfrequencies. Also, the calculation of the vibrational frequencies leads to the evaluation of zero-point energies (ZPEs). The counterpoise (CP) method [52] has been used to take into account thebasis set superposition error (BSSE) in the calculation of the energies and presents the energieswithout any BSSEs. Finally, the quantum theory of atoms in the molecules analysis [53] wasperformed with the help of the AIM 2000 software [54] using the wave functionals generated atthe MP2/cc-pVDZ level.

3. Results and discussion

The electronic structures of the isolated HNCS and SSO monomers were used to generate a setof heterodimers on the singlet PES. Note that the symbol A stands for the heterodimers of theHNCS–SSO system and the numbering of the symbolA conforms to the ordering of binding energy(corrected with BSSE and ZPE at the MP2/aug-cc-pVTZ//MP2/cc-pVDZ level). The optimizedgeometries of all the heterodimers and their ranking are reported in Figures 1 and 2, respectively.Also, the calculated binding energies and bond critical point data for different heterodimers in theMP2 level were listed in Tables 1 and 2, respectively. Note that the standard orientations of all het-erodimers of the HNCS–SSO system at the MP2/cc-pVDZ level and more details of energies are inTables S1 and S2 of supporting information (http://dx.doi.org/10.1080/17415993.2014.917376).

Association of the HNCS and the SSO monomers leads to the formation of nine minima, A1throughA9, on the singlet PES. Binding energies of the HNCS–SSO heterodimers including BSSEand ZPE corrections lie in the range of 5.23–19.12 kJ/mol at the MP2/aug-cc-pVTZ//MP2/cc-pVDZ level.

Figure 1. Optimized geometries of all the heterodimers in the HNCS–SSO system at the MP2/cc-pVDZ level (the bondlengths are in angstrom).

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Figure 2. The ranking of the heterodimers obtained in the HNCS–SSO system in terms of EI + BSSE + ZPE at theMP2/aug-cc-pVTZ//MP2/cc-pVDZ level.

Table 1. Binding energies (kJ/mol) of heterodimers obtained in theHNCS–SSO system at the MP2 level.

Optimization Single-point energySpecies MP2/cc-pVDZ MP2/aug-cc-pVTZ//MP2/cc-pVDZ

EI EI EI + BSSE EI + BSSE + ZPE

A1 −34.24 −28.68 −24.46 −19.12A2 −13.92 −20.80 −17.91 −15.68A3 −26.96 −22.33 −18.62 −14.16A4 −11.42 −15.79 −12.98 −10.43A5 −14.55 −16.52 −13.21 −10.24A6 −13.63 −14.92 −11.69 −8.83A7 −10.45 −10.35 −8.17 −6.17A8 −10.35 −10.19 −8.01 −6.09A9 −9.35 −8.41 −6.59 −5.23

A1 is the most stable heterodimer of the HNCS–SSO system with a binding energy 19.12 kJ/molafter corrections of BSSE and ZPE at the MP2/aug-cc-pVTZ//MP2/cc-pVDZ level. Figure 1shows that the planar heterodimer of A1 forms when O- and S3-atoms of the SSO monomer

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Table 2. Interatomic distances (Å) and bond critical point data (a.u.) calculated at theMP2/cc-pVDZ level.

Heterodimers Interaction Interatomic distance ρ ∇2ρ −GC/VC

A1 O…H 1.890 0.0256 0.1034 1.1602S3…N 3.806 0.0043 0.0129 1.2517

A2 S2…S1 3.602 0.0073 0.0188 1.2994S3…N 3.300 0.0091 0.0244 1.1397

A3 O…H 1.897 0.0246 0.1003 1.1684A4 S2…N 3.126 0.0103 0.0312 1.1978

O…C 3.204 0.0067 0.0218 1.2048A5 S3…H 2.626 0.0119 0.0309 1.0967A6 S3…H 2.596 0.0124 0.0327 1.1025A7 O…S1 3.135 0.0084 0.0312 1.1769

S3…S1 3.930 0.0045 0.0114 1.1815A8 O…S1 3.132 0.0085 0.0314 1.1765

S3…S1 3.965 0.0043 0.0111 1.1801A9 O…S1 3.212 0.0074 0.0280 1.2035

attack H- and N-atoms of the HNCS monomer to create the interactions of O…H and S3…N,respectively. The bond lengths of the interactions of O…H and S3…N are 1.890 and 3.806Å atthe MP2/cc-pVDZ level, respectively.

As shown in Table 2, binding energy of the A2 heterodimer is only 3.44 kJ/mol less than that ofthe A1 heterodimer at the MP2/aug-cc-pVTZ//MP2/cc-pVDZ level. The atomic connectivity ofthe A2 heterodimer is similar to the A1. Both of A1 and A2 heterodimers include intermolecularinteraction of S3…N. Their main difference is the second interaction. In the A2 heterodimer, theS2-atom of the SSO reacts with the Sl-atom of the HNCS monomer (S2…S1 interaction), whilein the A1 heterodimer, the O-atom of the SSO attacks the H-atom of the HNCS monomer (O…Hinteraction). This means that the replacement of the S2…S1 interaction in the A2 heterodimerwith the O…H interaction creates a more stable heterodimer of the A1.

A3 heterodimer includes only one interaction between the SSO and the HNCS monomers onPES. In theA3 heterodimer, O-atom of the SSO approaches H-atom of the HNCS monomer to formO…H interaction with bond length 1.897Å. This heterodimer has binding energy 14.16 kJ/mol(corrected with BSSE and ZPE) at the MP2/aug-cc-pVTZ//MP2/cc-pVDZ level. Note that theO…H interaction of the A3 heterodimer is slightly longer than that of the A1 as given in Table 2.

A4 heterodimer has the fourth stability order among nine heterodimers obtained for the HNCS–SSO system. It lies 10.43 kJ/mol below the initial monomers of the HNCS and the SSO. It isinteresting to say that two interactions of O…C (3.204Å) and S2…N (3.126Å) have been observedonly in the A4 heterodimer.

The comparison of theA5 andA6 heterodimers shows that atomic connectivity of them is equal.In both of them, the S3-atom of the SSO monomer reacts with the H-atom of the HNCS monomerto produce the S3…H interaction. In spite of similar atomic connectivity, the A5 heterodimer(10.24 kJ/mol) is 1.41 kJ/mol stable than A6 (8.83 kJ/mol) at the MP2/aug-cc-pVTZ//MP2/cc-pVDZ level. The calculated results include that the S…H interaction exists only in two the A5and A6 heterodimers.

Similar to the A5 and the A6 heterodimers, the atomic connectivity of the A7 heterodimer isexactly similar to that of A8. Both of them include two interactions of O…S1 and S3…S1 asshown in Figure 1. Precise investigation of the situation of the HNCS H-atom relative to the SSOmonomer in the A7 and A8 heterodimers reveals that it is suitable to use trans and cis terms forthe A7 and the A8 heterodimers, respectively. The binding energies of the A7 and the A8 are 6.17and 6.09 kJ/mol at the MP2/aug-cc-pVTZ//MP2/cc-pVDZ level.

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A9 heterodimer is the least stable heterodimer of the HNCS–SSO system with the bindingenergy 5.23 kJ/mol (corrected with BSSE and ZPE). The attack of the SSO terminal atom on theS1-atom of the HNCS monomer leads to the O…S1 interaction with the bond length 3.212Å inthe A9 heterodimer.

Wierzejewska and Wieczorek [25] studied the intermolecular interactions of the HNCS–N2

and HNCS–Xe systems at the MP2 level. They reported the existence of two and one stable com-plexes for the HNCS–N2 and HNCS–Xe systems, respectively. The comparison of our resultswith those of Wierzejewska et al. includes three important points. Firstly, the number of het-erodimers reported for the HNCS–SSO system in the present work (nine heterodimers) is muchmore than those of Wierzejewska et al. for the HNCS–N2 (two heterodimers) and HNCS–Xe(one heterodimer) systems. Secondly, the binding energy of the most stable heterodimer (A1) ofthe HNCS–SSO system corrected with only BSSE (24.46 kJ/mol) is much more than that of theHNCS–N2 (6.68 kJ/mol) and the HNCS–Xe (3.64 kJ/mol) systems. This means that the HNCS–SSO system has more important influence than the HNCS–N2 and the HNCS–Xe systems in theatmosphere. Thirdly, the most stable heterodimers obtained for two systems of the HNCS–N2

and the HNCS–Xe [25] involve an interaction from HN group of the HNCS molecule with eitherthe N2 molecule (in the HNCS–N2 system) or Xe (in the HNCS–Xe system). This is in goodagreement with intermolecular interactions obtained for the A1 heterodimers as the most stableheterodimers of the HNCS–SSO system in the present work.

As shown in Figure 2, the binding energies corrected with BSSE and ZPE for all the het-erodimers obtained in the HNCS–SSO system have been ranked to provide overall insight intobetween the binding energies and intermolecular interaction. It can be seen that all three unstableheterodimers of the HNCS–SSO system (A7, A8 and A9) include only an interactions betweenthe terminal sulfur atom of the HNCS monomer (denoted as S1) with the SSO monomer. Also,three heterodimers of A3, A5 and A6 have only one interaction between the HNCS and the SSOmonomers. As shown in Figure 2, the H-atom interaction of the HNCS with the O-atom of theSSO monomer (in the A3 heterodimer) creates a more stable complex relative to the H-atominteraction of the HNCS with the S-atom of the SSO monomer (in the A5 and A6 heterodimers).

It is necessary to say that all the possible intermolecular interactions in the of the HNCS–SSOsystem have been found in the present work except four interactions of O…N, S2…H, S2…C andS3…C. This means that none of the HNCS–SSO heterodimers include an interaction betweeneither the S-atom of the SSO (S2 or S3) and the C-atom of the HNCS monomer or the O-atom ofthe SSO and the N-atom of the HNCS monomer.

3.1. AIM analysis

TheAIM theory [53] has been used in order to analyze the electron density (ρ) of the heterodimers.According to this analysis, ρ is used to describe the strength of a bond. In general, the larger thevalue of ρ is, the stronger the bond is. The Laplacian of the electron density (∇2ρ) describes thecharacteristic of the bond. Where ∇2ρ < 0 the bond is a covalent bond, as ∇2ρ > 0, the bondbelongs to the ionic bond, hydrogen bond and van der Waals interaction. The GC/VC ratio, beingGC and VC, respectively, the kinetic and potential energy density at bond critical point (BCP), wasused as a measure of the covalency in non-covalent interactions. Values greater than 1 generallyindicate a non-covalent interaction without covalent character while ratios smaller than unity areindicative of the covalent nature of the interaction.[55,56] The values of topological parameters(ρ, ∇2ρ and GC/VC) for each intermolecular BCPs between the HNCS and the SSO monomersare given in Table 2.

As shown in Table 2, ρ values are in the range of 0.0043–0.0256 a.u. It is interesting to knowthat the biggest value of ρ between the intermolecular interactions of the HNCS–SSO system

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belongs to the O…H interaction in the A1 heterodimer (0.0256 a.u.). While the smallest ρ valuebelongs to the S3…N (in the A1 with 0.0043 a.u.) and S3…S1 (in the A8 with 0.0043 a.u.)interactions. The investigation of values obtained for ∇2ρ in the HNCS–SSO system shows thatall of them are positive and should be within the range of 0.0111–0.1034 a.u. All values reportedfor the −GC/VC ratio of heterodimers in the HNCS–SSO system is greater than 1, as given inTable 2. Therefore, the small electron density and positive values of ∇2ρ with −GC/VC > 1 areindicating that all intermolecular interactions in the HNCS–SSO system are weak interactions ofnon-covalent without any covalent characters.

4. Conclusions

The present work reports a study of the structural and electronic properties of heterodimersbetween the HNCS and the SSO monomers on the singlet PES, theoretically. The calculatedresults show that the attack of the HNCS on the SSO monomer leads to formation of nine min-ima, A1 through A9. Their binding energies (corrected with BSSE and ZPE) lie in the range of5.23–19.12 kJ/mol at the MP2/aug-cc-pVTZ//MP2/cc-pVDZ level. All possible intermolecularinteractions in the HNCS–SSO system have been found in the present work except four interac-tions of O…N, S2…H, S2…C and S3…C. The calculated results reveal that the heterodimerscontaining only interactions between the terminal sulfur atom of the HNCS monomer (denotedas S1) with the SSO monomer (A7, A8 and A9) have the least binding energy in the HNCS–SSOsystem. Also, the binding energy of the individual interaction of the HNCS H-atom with theO-atom of the SSO monomer (in the A3 heterodimer) is bigger than the individual interaction ofthe HNCS H-atom with the S-atom of the SSO monomer (in the A5 and A6 heterodimers). Thecomparison of the binding energies of the HNCS–SSO system (the present work) with those ofHNCS–N2 and the HNCS–Xe systems (Wierzejewska et al.) shows that the heterodimers of theHNCS–SSO system are much more stable that the heterodimers obtained in both of the HNCS–N2

and the HNCS–Xe systems. Based on the AIM analysis, the small electron density, positive valuesof ∇2ρ and −GC/VC > 1 indicate that all intermolecular interactions in the HNCS–SSO systemare weak interactions of non-covalent without any covalent characters.

Supplemental data

Supplemental data for this article can be accessed at 10.1080/17415993.2014.917376.

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