An integrated computational approach built on quantum mechanical (QM) methods, purposely tailored interand intra-molecular force fields and continuum solvent models combined with time-independent and timedependent schemes to account for nuclear motion effects is applied to the spectroscopic investigation of pyrimidine in the gas phase as well as in aqueous and CCl4 solutions. Accurate post-Hartree–Fock methodologies are employed to compute molecular structure, harmonic vibrational frequencies, energies and oscillator strengths for electronic transitions in order to validate the accuracy of approaches rooted into density functional theory with emphasis also on hybrid QM/QM′ models. Within the time-independent approaches,IR spectra are computed including anharmonicities through perturbative corrections while UV–vis line-shapes are simulated accounting for the vibrational structure; in both cases, the environmental effects are described by continuum models. The effects of conformational flexibility, including solvent dynamics, are describedthrough time-dependent models based on purposely DFT-tailored force fields applied to molecular dynamics simulations and on QM computations of spectroscopic properties. Such procedures are exploited to simulate IR and UV–vis spectra of pyrimidine in the gas phase and in solutions, leading in all cases to good agreementwith experimental observations and allowing to dissect different effects underlying spectral phenomena.

Integrated computational approaches for spectroscopic studies of molecular systems in the gas phase and in solution: pyrimidine as a test case / M., Biczysko; J., Bloino; G., Brancato; I., Cacelli; C., Cappelli; A., Ferretti; A., Lami; S., Monti; Pedone, Alfonso; G., Prampolini; C., Puzzarini; F., Santoro; F., Trani; G., Villani. - In: THEORETICAL CHEMISTRY ACCOUNTS. - ISSN 1432-881X. - ELETTRONICO. - 131:(2012), pp. 1201-1219. [10.1007/s00214-012-1201-3]

Integrated computational approaches for spectroscopic studies of molecular systems in the gas phase and in solution: pyrimidine as a test case.

PEDONE, Alfonso;
2012

Abstract

An integrated computational approach built on quantum mechanical (QM) methods, purposely tailored interand intra-molecular force fields and continuum solvent models combined with time-independent and timedependent schemes to account for nuclear motion effects is applied to the spectroscopic investigation of pyrimidine in the gas phase as well as in aqueous and CCl4 solutions. Accurate post-Hartree–Fock methodologies are employed to compute molecular structure, harmonic vibrational frequencies, energies and oscillator strengths for electronic transitions in order to validate the accuracy of approaches rooted into density functional theory with emphasis also on hybrid QM/QM′ models. Within the time-independent approaches,IR spectra are computed including anharmonicities through perturbative corrections while UV–vis line-shapes are simulated accounting for the vibrational structure; in both cases, the environmental effects are described by continuum models. The effects of conformational flexibility, including solvent dynamics, are describedthrough time-dependent models based on purposely DFT-tailored force fields applied to molecular dynamics simulations and on QM computations of spectroscopic properties. Such procedures are exploited to simulate IR and UV–vis spectra of pyrimidine in the gas phase and in solutions, leading in all cases to good agreementwith experimental observations and allowing to dissect different effects underlying spectral phenomena.
131
1201
1219
Integrated computational approaches for spectroscopic studies of molecular systems in the gas phase and in solution: pyrimidine as a test case / M., Biczysko; J., Bloino; G., Brancato; I., Cacelli; C., Cappelli; A., Ferretti; A., Lami; S., Monti; Pedone, Alfonso; G., Prampolini; C., Puzzarini; F., Santoro; F., Trani; G., Villani. - In: THEORETICAL CHEMISTRY ACCOUNTS. - ISSN 1432-881X. - ELETTRONICO. - 131:(2012), pp. 1201-1219. [10.1007/s00214-012-1201-3]
M., Biczysko; J., Bloino; G., Brancato; I., Cacelli; C., Cappelli; A., Ferretti; A., Lami; S., Monti; Pedone, Alfonso; G., Prampolini; C., Puzzarini; F., Santoro; F., Trani; G., Villani
File in questo prodotto:
Non ci sono file associati a questo prodotto.
Pubblicazioni consigliate

Caricamento pubblicazioni consigliate

Licenza Creative Commons
I metadati presenti in IRIS UNIMORE sono rilasciati con licenza Creative Commons CC0 1.0 Universal, mentre i file delle pubblicazioni sono rilasciati con licenza Attribuzione 4.0 Internazionale (CC BY 4.0), salvo diversa indicazione.
In caso di violazione di copyright, contattare Supporto Iris

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11380/712192
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 64
  • ???jsp.display-item.citation.isi??? 62
social impact