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Quantum mechanical computations and spectroscopy: From small rigid molecules in the gas phase to large flexible molecules in solution (55 views)

Barone V, Improta R, Rega N

Acc Chem Res (ISSN: 0001-4842), 2008 May; 41(5): 605-616.

Abstract
(Figure Presented) Interpretation of structural properties and dynamic behavior of molecules in solution is of fundamental importance to understand their stability, chemical reactivity, and catalytic action. While information can be gained, in principle, by a variety of spectroscopic techniques, the interpretation of the rich indirect information that can be inferred from the analysis of experimental spectra is seldom straightforward because of the subtle interplay of several different effects, whose spedfic role is not easy to separate and evaluate. In such a complex scenario, theoretical studies can be very helpful at two different levels: (i) supporting and complementing experimental results to determine the structure of the target molecule starting from its spectral properties; (ii) dissecting and evaluating the role of different effects in determining the observed spedroscopic properties. This is the reason why computational spectroscopy is rapidly evolving from a highly spedalized research field into a versatile and widespread tool for the assignment of experimental spectra and their interpretation in terms of chemical physical effects. In such a situation, it becomes important that both computationally and experimentally oriented chemists are aware that new methodological advances and integrated computational strategies are available, providing reliable estimates of fundamental spectral parameters not only for relatively small molecules in the gas phase but also for large and flexible molecules in condensed phases. In this Account, we review the most significant methodological contributions from our research group in this field, and by exploiting some recent results of their application to the computation of IR, UV-vis, NMR, and EPR spectral parameters, we discuss the microscopic mechanisms underlying solvent and vibrational effects on the spectral parameters. After reporting some recent achievements for the study of excited states by first prindple quantum mechanical approaches, we focus on the treatment of environmental effects by means of mixed discrete-continuum solvent models and on effective methods for computing vibronic contributions to the spectra. We then discuss some new developments, mainly based on time-dependent approaches, allowing us to go beyond the determination of spectroscopic parameters toward the simulation of line widths and shapes. Although further developments are surely needed to improve the accuracy and effectiveness of several items in the proposed approach, we try to show that the first important steps toward a direct comparison between the results obtained in vitro and those obtained in silico have been made, making easier fruitful crossovers among experiments, computations and theoretical models, which would be dedsive for a deeper understanding of the spectral behavior assodated with complex systems and processes. © 2008 American Chemical Society.

Affiliations ▼
*** IBB - CNR Affiliation

Chemistry Department Paolo Corradini, University Federico II, Complesso Universitario Monte S. Angelo, via Cintia, I-80126 Napoli, Italy

Details ▼
Impact factor: 12.176, 5-year impact factor: 15.403

Paper type: Journal Article,

Keywords: Not available.

Url: http://www.scopus.com/inward/record.url?eid=2-s2.0-45749092976&partnerID=40&md5=fb9a10f9abaed7011ae30addc479a6eb

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* Absorption and fluorescence spectra of uracil in the gas phase and in aqueous solution: A TD-DFT quantum mechanical study (115 views)
Improta R, Barone V
J Am Chem Soc (ISSN: 0002-7863, 0002-2786, 1520-5126), 2004 Nov 10; 126(44): 14320-14321.

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1 Records (1 excluding Abstracts and Conferences).
Total impact factor: 6.903 (6.903 excluding Abstracts and Conferences).
Total 5-year impact factor: 11.015 (11.015 excluding Abstracts and Conferences).



Your bibliography query: (([btitle, keywords, abstract] QUANTUM AND [btitle, keywords, abstract] MECHANICAL AND [btitle, keywords, abstract] COMPUTATIONS AND [btitle, keywords, abstract] SPECTROSCOPY AND [btitle, keywords, abstract] FROM)) AND NOT [id] = 9209



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