A comparative study of the structure and bonding of HOO, HOS, HSO, and HSS radicals by <scp>CNDO</scp>/2 and <scp>INDO</scp> methods

De, B. K.; Sannigrahi, A. B.

doi:10.1002/jcc.540010404

Cited by 11 publications

(4 citation statements)

References 33 publications

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“…In particular, it may be involved in a so-called catalytic cycle [8][9][10] for destruction of ozone in the troposphere, namely There have been numerous experimental and theoretical studies of the HSO and HOS isomers. [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28] Ab initio calculations for the HSO and HOS radicals were first reported by Sannigrahi et al, 26 who predicted HOS to be more stable than HSO. Several ab initio calculations 7 have been reported afterward which corroborated such a prediction, although the magnitude of the energy difference between the minima associated with these species was found to decrease with improvement in the quality of the calculations.…”

Section: Introductionmentioning

confidence: 99%

Single-Valued DMBE Potential Energy Surface for HSO: A Distributed n-Body Polynomial Approach

Martı́nez-Núñez

Varandas

2001

J. Phys. Chem. A

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An accurate single-valued double many-body expansion (DMBE) potential energy surface is reported for the ground electronic state of HSO based on novel MR CISD ab initio energies suitably corrected for the complete one-electron basis set/complete CI limit. To improve the accuracy of the fit, we have suggested a n-body distributed polynomial approach which implies using individual multinomial developments at the various stationary points. For simplicity, only the three most relevant such points have been considered: two minima (HSO, HOS) and the saddle point connecting them.

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Section: Introductionmentioning

confidence: 99%

Single-Valued DMBE Potential Energy Surface for HSO: A Distributed n-Body Polynomial Approach

Martı́nez-Núñez

Varandas

2001

J. Phys. Chem. A

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“…Investigation on the structure, spectrum, and dynamics of the electronic states of the HSO radical is thus of pivotal importance to understand the reactions and photochemical processes involving sulfur-containing species, which has attracted many experimental ,− and theoretical − studies during the past decades. The first theoretical study could be dated back to over 35 years ago by Sannigrahi et al, in which the geometries of the electronic ground state and the first excited state were predicted. , Several high-level ab initio calculations have been performed since then, focusing on the low-lying electronic states of the HSO radical. ,, Experimentally, the transition between the electronic ground state 2 A″ and the excited state 2 A′ for HSO was first reported by Schurath et al Later, Kakimoto et al and Ohashi et al studied the vibronic spectra of the HSO and DSO radicals via Doppler-limited laser excitation spectroscopy to determine accurate molecular constants of the ground and the excited states.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Investigation on Electronic Excited States of the HSO Radical

Li,

Xiao,

Bian

et al. 2024

J. Phys. Chem. A

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HSO radicals play an important role in the photochemical processes in combustion, the atmosphere, and the interstellar medium. In this work, we perform a high-level ab initio study on the electronic excited states of HSO using the internally contracted multireference configuration interaction methods including Davidson correction (icMRCI + Q) in combination with the correlation-consistent basis sets. The molecular geometries, vertical transition energies, oscillator strengths, and electronic configurations of 19 electronic states of HSO are computed. The electronic potential energy curves of HSO along the bond lengths and bond angles are presented. Based on our calculations, the interactions between the electronic states involved in the ultraviolet region and the mechanism of photodissociation are discussed, which will lay a foundation for revealing the dissociation dynamics of gas-phase HSO molecules in outer space and the earth’s atmosphere.

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“…Most hydrogen bonds of the studies examine complexes formed exclusively made up of closed shell molecules, such as studies of the water dimer 10. HOO and HSO radicals are important molecules involved in atmospheric, combustion, and biological processes 11–19. It is known that the HOO radical reacts with formaldehyde 20.…”

Section: Introductionmentioning

confidence: 99%

Theoretical study of the SH···O blue‐shifted hydrogen bond

Yang

2008

Int J of Quantum Chemistry

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ABSTRACT:Theoretical calculations were performed to study the nature of the hydrogen bonds in the complexes HCHO⅐⅐⅐HSO, HCOOH⅐⅐⅐HSO, HCHO⅐⅐⅐HOO, and HCOOH⅐⅐⅐HOO. The geometric structures and vibrational frequencies of these four complexes at the MP2/6-31G(d,p) and MP2/6-311ϩG(d,p) levels are calculated by standard and counterpoise-corrected methods, respectively. The results indicate that in the complexes HCHO⅐⅐⅐HSO and HCOOH⅐⅐⅐HSO the SOH bond is strongly contracted. In the SOH⅐⅐⅐O hydrogen bonds, the calculated blue shifts for the SOH stretching frequencies are in the vicinity of 50 cm Ϫ1. While in the complexes HCHO⅐⅐⅐HOO and HCOOH⅐⅐⅐HOO, the OOH bond is elongated and OOH⅐⅐⅐O red-shifted hydrogen bonds are found. From the natural bond orbital analysis it can be seen that the XOH bond length in the XOH⅐⅐⅐Y hydrogen bond is controlled by a balance of four main factors in the opposite directions: hyperconjugation, electron density redistribution, rehybridization, and structural reorganization. Among them hyperconjugation has the effect of elongating the XOH bond. Electron density redistribution and rehybridization belong to the bond shortening effects, while structural reorganization has an uncertain influence on the XOH bond length. In the complexes HCHO⅐⅐⅐HSO and HCOOH⅐⅐⅐HSO, the shortening effects dominate which lead to the blue shift of the SOH stretching frequencies. In the complexes HCHO⅐⅐⅐HOO and HCOOH⅐⅐⅐HOO where elongating effects are dominant, the OOH⅐⅐⅐O hydrogen bonds are red-shifted.

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A comparative study of the structure and bonding of HOO, HOS, HSO, and HSS radicals by CNDO/2 and INDO methods

Cited by 11 publications

References 33 publications

Single-Valued DMBE Potential Energy Surface for HSO: A Distributed n-Body Polynomial Approach

Single-Valued DMBE Potential Energy Surface for HSO: A Distributed n-Body Polynomial Approach

Theoretical Investigation on Electronic Excited States of the HSO Radical

Theoretical study of the SH···O blue‐shifted hydrogen bond

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