TY - JOUR

T1 - Spectral Diagnostics of the Dynamics of the Formation of a Homoconjugated Complex [HCN.H.NCH]+

AU - Denisov, G. S.

AU - Melikova, S. M.

AU - Rutkovskii, K. S.

AU - Tokhadze, K. G.

N1 - Funding Information: This work was supported by the Russian Foundation for Basic Research, project no. 17-03-00590. Funding Information: The calculations were carried out using the equipment of the Resource Computational Center of the St. Petersburg State University (http://cc.spbu.ru). Publisher Copyright: © 2020, Pleiades Publishing, Ltd. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2020/4/1

Y1 - 2020/4/1

N2 - Abstract: A quantum-mechanical analysis of the manifestations of the NHN hydrogen bond in the vibrational spectra of the [HCN.H.NCH]+ linear complex along the profile of the proton transition reaction path is given, and the laws governing the diagnostic parameters, that is, potential descriptors of the dynamics of this process, are determined. We calculated the surface of the potential energy and harmonic frequencies of normal vibrations along the profile of the reaction path of the proton transition in the system under study. When the fragments [HCNH]+ and NCH approach each other, a noticeable distortion of the forms of their skeletal vibrations occurs, up to complete mixing into the symmetric and antisymmetric forms. The frequency of the longitudinal vibration of the central proton ν(NH) varies along the reaction path from ~3600 to ~500 cm–1. An abrupt frequency change is observed in the region of intersection of the terms ν(NH) and ν(CN).

AB - Abstract: A quantum-mechanical analysis of the manifestations of the NHN hydrogen bond in the vibrational spectra of the [HCN.H.NCH]+ linear complex along the profile of the proton transition reaction path is given, and the laws governing the diagnostic parameters, that is, potential descriptors of the dynamics of this process, are determined. We calculated the surface of the potential energy and harmonic frequencies of normal vibrations along the profile of the reaction path of the proton transition in the system under study. When the fragments [HCNH]+ and NCH approach each other, a noticeable distortion of the forms of their skeletal vibrations occurs, up to complete mixing into the symmetric and antisymmetric forms. The frequency of the longitudinal vibration of the central proton ν(NH) varies along the reaction path from ~3600 to ~500 cm–1. An abrupt frequency change is observed in the region of intersection of the terms ν(NH) and ν(CN).

KW - hydrogen bond

KW - isotope effect

KW - proton transition

KW - vibrational spectrum

UR - http://www.scopus.com/inward/record.url?scp=85084922041&partnerID=8YFLogxK

U2 - 10.1134/S0030400X20040062

DO - 10.1134/S0030400X20040062

M3 - Article

AN - SCOPUS:85084922041

VL - 128

SP - 467

EP - 469

JO - OPTICS AND SPECTROSCOPY

JF - OPTICS AND SPECTROSCOPY

SN - 0030-400X

IS - 4

ER -