We introduce a quantum mechanics/molecular mechanics semiclassical method for studying the solvation process of molecules in water at the nuclear quantum mechanical level with atomistic detail. We employ it in vibrational spectroscopy calculations because this is a tool that is very sensitive to the molecular environment. Specifically, we look at the vibrational spectroscopy of thymidine in liquid water. We find that the C=O frequency red shift and the C=C frequency blue shift, experienced by thymidyne upon solvation, are mainly due to reciprocal polarization effects, that the molecule and the water solvent exert on each other, and nuclear zero-point energy effects. In general, this work provides an accurate and practical tool to study quantum vibrational spectroscopy in solution and condensed phase, incorporating high-level and computationally affordable descriptions of both electronic and nuclear problems.

Unraveling Water Solvation Effects with Quantum Mechanics/Molecular Mechanics Semiclassical Vibrational Spectroscopy: The Case of Thymidine / D. Moscato, G. Mandelli, M. Bondanza, F. Lipparini, R. Conte, B. Mennucci, M. Ceotto. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - 146:12(2024 Mar 27), pp. 8179-8188. [10.1021/jacs.3c12700]

Unraveling Water Solvation Effects with Quantum Mechanics/Molecular Mechanics Semiclassical Vibrational Spectroscopy: The Case of Thymidine

D. Moscato
Primo
;
G. Mandelli
Secondo
;
R. Conte;M. Ceotto
Ultimo
2024

Abstract

We introduce a quantum mechanics/molecular mechanics semiclassical method for studying the solvation process of molecules in water at the nuclear quantum mechanical level with atomistic detail. We employ it in vibrational spectroscopy calculations because this is a tool that is very sensitive to the molecular environment. Specifically, we look at the vibrational spectroscopy of thymidine in liquid water. We find that the C=O frequency red shift and the C=C frequency blue shift, experienced by thymidyne upon solvation, are mainly due to reciprocal polarization effects, that the molecule and the water solvent exert on each other, and nuclear zero-point energy effects. In general, this work provides an accurate and practical tool to study quantum vibrational spectroscopy in solution and condensed phase, incorporating high-level and computationally affordable descriptions of both electronic and nuclear problems.
QM/MM; semiclassical; ab initio; thymidine
Settore CHIM/02 - Chimica Fisica
Settore FIS/03 - Fisica della Materia
   A web-platform interfaced software for spectroscopic molecular characterization and early diagnosis of Parkinson's disease (SEMISOFT)
   SEMISOFT
   EUROPEAN COMMISSION
   101081361

   Divide and Conquer ad initio semiclassical molecular dynamics for spectropic calculations of complex systems (SEMICOMPLEX)
   SEMICOMPLEX
   EUROPEAN COMMISSION
   H2020
   647107

   Light-Induced Function: from Excitation to Signal through Time and Space
   LIFETimeS
   European Commission
   Horizon 2020 Framework Programme
   786714
27-mar-2024
12-mar-2024
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/1044476
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