2015
DOI: 10.1021/acs.jpca.5b07585
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Anharmonicity Effects in IR Spectra of [Re(X)(CO)3(α-diimine)] (α-diimine = 2,2′-bipyridine or pyridylimidazo[1,5-a]pyridine; X = Cl or NCS) Complexes in Ground and Excited Electronic States

Abstract: Infrared spectra of [Re(X)(CO)(3)(α-diimine)] (α-diimine = 2,2'-bipyridine, X = Cl, NCS, or pyridylimidazo[1,5-a]pyridine, X = Cl) in the ground and the lowest triplet electronic states were calculated by a global hybrid density functional going beyond the harmonic level by means of second-order vibrational perturbation theory (VPT2) and including bulk solvent effects by the polarizable continuum model (PCM). The full-dimensionality (FD) VPT2 is compared with the reduced-dimensionality (RD) model, where only s… Show more

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Cited by 19 publications
(21 citation statements)
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“…In order to extend accurate anharmonic computations to larger systems we recall that the B2D3 harmonic wavenumbers are often more computationally demanding (mainly due to the increased memory requirements) than the evaluation of anharmonic corrections at the B3D3 level. Moreover, anharmonic corrections within reduced dimensionality schemes46,105,106 can be quite routinely computed also for rather large systems like, for instance, uracil heptamer34, chlorophyll105,107, glycine adsorbed on silicon cluster106 or metal-carbonyl-diimine complexes108. All these systems feature spectral fingerprints due to the carbonyl and/or amino groups, clearly showing that it would be highly desirable to correct ν (C=O) and ν (N-H) harmonic wavenumbers, also when B2D3 computations become unfeasible.…”
Section: Resultsmentioning
confidence: 99%
“…In order to extend accurate anharmonic computations to larger systems we recall that the B2D3 harmonic wavenumbers are often more computationally demanding (mainly due to the increased memory requirements) than the evaluation of anharmonic corrections at the B3D3 level. Moreover, anharmonic corrections within reduced dimensionality schemes46,105,106 can be quite routinely computed also for rather large systems like, for instance, uracil heptamer34, chlorophyll105,107, glycine adsorbed on silicon cluster106 or metal-carbonyl-diimine complexes108. All these systems feature spectral fingerprints due to the carbonyl and/or amino groups, clearly showing that it would be highly desirable to correct ν (C=O) and ν (N-H) harmonic wavenumbers, also when B2D3 computations become unfeasible.…”
Section: Resultsmentioning
confidence: 99%
“…A remarkable example showing the effectiveness of the RD model is offered by time-resolved infrared spectroscopy (TRIR) studies of photoinduced processes in metal-carbonyl-diimine complexes 122. Electronic and structural changes in these systems can be effectively monitored by the changes in band positions and intensities of carbonyl stretching vibrations ν (C=O), which show very strong, isolated IR bands around 2000 cm −1 .…”
Section: Toward Larger and Flexible Molecular Systemsmentioning
confidence: 99%
“… a All computations at the B3LYP/6-31+G(d)/Re-(8s7p6d2f1g)/[6s5p3d2f1g]PP/PCM(CH 2 Cl 2 ) level, see Ref 122. for details. b Symmetry labels of approximate C s symmetry in parenthesis. …”
Section: Figurementioning
confidence: 99%
“…32 The B3LYP 33,34 exchange–correlation functional was adopted, in conjunction with the 6-31+G* basis set 35 (see also ref. 36).…”
Section: Experimental Methods and Computational Detailsmentioning
confidence: 99%