Publication:
Parametric Broadening of the Electronic-Vibrational Spectrum of a Molecule Caused by Zero-Point Vibrations and Thermal Fluctuations of Interatomic Bonds

Дата
2021
Авторы
Lebedev-Stepanov, P. V.
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Организационные подразделения
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Институт нанотехнологий в электронике, спинтронике и фотонике
Институт ИНТЭЛ занимается научной деятельностью и подготовкой специалистов в области исследования физических принципов, проектирования и разработки технологий создания компонентной базы электроники гражданского и специального назначения, а также построения современных приборов на её основе. ​Наша основная цель – это создание и развитие научно-образовательного центра мирового уровня в области наноструктурных материалов и устройств электроники, спинтроники, фотоники, а также создание эффективной инновационной среды в области СВЧ-электронной и радиационно-стойкой компонентной базы, источников ТГц излучения, ионно-кластерных технологий материалов.​
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© 2021, Pleiades Publishing, Ltd.Abstract: The existence in the Born–Oppenheimer approximation of a fundamentally new type of broadening of the spectral line of the electronic vibrational–rotational (rovibronic) transition in a molecule, caused by zero-point vibrations and thermal fluctuations of atomic nuclei near their equilibrium positions during vibrational–rotational motion inside the molecule, is discovered. A quantitative description in the harmonic approximation is obtained to describe the shape and width of the electron transition line corresponding to this type of broadening, which is called parametric, since the energy of any rovibronic level and transition between levels depends parametrically on the current instantaneous position of nuclei, which move much more slowly than electrons. To take this effect into account, Franck-Condon diagrams with oblique (bent) levels of vibrational energy are proposed. From the point of view of the Copenhagen interpretation of quantum mechanics, the parametric broadening exists due to the difference between an open (i.e. experimentally measured) quantum system from an isolated (unobservable) one. The magnitude of this broadening is estimated on the example of the 0–0 transition in a series of polymethine dye monomers. The estimate showed that the magnitude of the parametric broadening of the indicated zero-phonon line is comparable with the broadening observed in the experiment. The existing quantum chemical methods for calculating molecular spectra do not take into account the parametric broadening. They smooth the quasi-continuum of closely spaced rovibronic transitions, approximately calculating their common envelope, but do not consider the broadening of a single transition. The creation of a theory of parametric broadening will contribute to the development of intramolecular converters of energy from nuclei to electrons and vice versa, sensing nanoprobes, and quantum radio, photoacoustic and acousto-optic, and transceiving or converting devices of molecular size.
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Lebedev-Stepanov, P. V. Parametric Broadening of the Electronic-Vibrational Spectrum of a Molecule Caused by Zero-Point Vibrations and Thermal Fluctuations of Interatomic Bonds / Lebedev-Stepanov, P.V. // Doklady Physics. - 2021. - 66. - № 10. - P. 277-284. - 10.1134/S1028335821100025
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https://www.doi.org/10.1134/S1028335821100025
 https://www.scopus.com/record/display.uri?eid=2-s2.0-85126188081&origin=resultslist
 http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=Alerting&SrcApp=Alerting&DestApp=WOS_CPL&DestLinkType=FullRecord&UT=WOS:000768427600002
 https://openrepository.mephi.ru/handle/123456789/25329
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