Solvent effects on the intensities of the weak ultraviolet spectra of ketones and nitroparaffins—I

Bayliss, N. S.; Wills-Johnson, G.

doi:10.1016/0584-8539(68)80087-x

Cited by 86 publications

(87 citation statements)

References 8 publications

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“…As before, the computed shift in water (1493 cm Ϫ1 ) is reasonable compared to the experimental data [16,17] ). For dioxane experiments [18] show no appreciable shift, while our value of ϩ54 cm Ϫ1 is reasonably close to zero.…”

Section: Solvochroism Of the P * ← N Transition Of Acetone Revisitedsupporting

confidence: 64%

“…) is excellent compared to the experimental value of Ϫ250 cm Ϫ1 reported by Hayes [17], but is too small in comparison to the shift observed by Bayliss (Ϫ450 cm Ϫ1 ) [16]. The uncertainties given in Table 1 are root mean square deviations over the 100 conformations analyzed, and therefore probably larger than in our earlier work.…”

contrasting

confidence: 37%

“…The uncertainties given in Table 1 are root mean square deviations over the 100 conformations analyzed, and therefore probably larger than in our earlier work. The values do not indicate the error in the maximum position of the transition, but rather reflect the broadness of the maxima mentioned by Bayliss [16]. In polar solvents the r.m.s.…”

mentioning

confidence: 99%

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Some applications of the direct reaction field approach

Duijnen¹,

Grozema²,

Swart³

1999

Journal of Molecular Structure: THEOCHEM

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Section: Solvochroism Of the P * ← N Transition Of Acetone Revisitedsupporting

confidence: 64%

contrasting

confidence: 37%

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Some applications of the direct reaction field approach

Duijnen¹,

Grozema²,

Swart³

1999

Journal of Molecular Structure: THEOCHEM

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“…The calculated acetone spectrum shows a solvent-induced blue shift for the n f π*; this is qualitatively consistent with the experimental results. 72 The averaged gas-phase and aqueousphase acetone n f π* vertical excitation energies and solventinduced shifts are compared in Table 5 with previous experimental measurements 70,71 and theoretical calculations. 30 The CIS/ EFP1 vertical excitation energies are overestimated, reflecting the approximate nature of the CIS method; however, the solventinduced shifts in the absorption spectrum predicted by CIS/ EFP1 are in qualitative agreement with the previous results.…”

Section: Resultsmentioning

confidence: 99%

Solvent-Induced Frequency Shifts: Configuration Interaction Singles Combined with the Effective Fragment Potential Method

et al. 2010

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The simplest variational method for treating electronic excited states, configuration interaction with single excitations (CIS), has been interfaced with the effective fragment potential (EFP) method to provide an effective and computationally efficient approach for studying the qualitative effects of solvents on the electronic spectra of molecules. Three different approaches for interfacing a non-self-consistent field (SCF) excited-state quantum mechanics (QM) method and the EFP method are discussed. The most sophisticated and complex approach (termed fully self consistent) calculates the excited-state electron density with fully self-consistent accounting for the polarization (induction) energy of effective fragments. The simplest approach (method 1) includes a strategy that indirectly adds the EFP perturbation to the CIS wave function and energy via modified Hartree−Fock molecular orbitals, so that there is no direct EFP interaction with the excited-state density. An intermediate approach (method 2) accomplishes the latter in a noniterative perturbative manner. Theoretical descriptions of the three approaches are presented, and test results of solvent-induced shifts using methods 1 and 2 are compared with fully ab initio values. These comparisons illustrate that, at least for the test cases examined here, modification of the ground-state Hartree−Fock orbitals is the largest and most important factor in the calculated solvent-induced shifts. Method 1 is then employed to study the aqueous solvation of coumarin 151 and compared with experimental measurements. PO Box 2206, Germantown, Maryland 20875 ReceiVed: February 27, 2010 ReVised Manuscript ReceiVed: May 20, 2010 The simplest variational method for treating electronic excited states, configuration interaction with single excitations (CIS), has been interfaced with the effective fragment potential (EFP) method to provide an effective and computationally efficient approach for studying the qualitative effects of solvents on the electronic spectra of molecules. Three different approaches for interfacing a non-self-consistent field (SCF) excited-state quantum mechanics (QM) method and the EFP method are discussed. The most sophisticated and complex approach (termed fully self consistent) calculates the excited-state electron density with fully self-consistent accounting for the polarization (induction) energy of effective fragments. The simplest approach (method 1) includes a strategy that indirectly adds the EFP perturbation to the CIS wave function and energy via modified Hartree-Fock molecular orbitals, so that there is no direct EFP interaction with the excited-state density. An intermediate approach (method 2) accomplishes the latter in a noniterative perturbative manner. Theoretical descriptions of the three approaches are presented, and test results of solvent-induced shifts using methods 1 and 2 are compared with fully ab initio values. These comparisons illustrate that, at least for the test cases examined here, modification of the groun...

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“…Robinson [3] formulated a theory for a single perturber at a fixed inter-nuclear distance with the solute and presented the mechanism by which the forbidden electronic intensity is enhanced by solvent perturbation. Bayliss and Will-Johnson [4] adapted Linder's [5] treatment of dispersion interaction between the solute and solvent by a rapidly oscillating electric field to formulate ''field simulation model''.…”

Section: Introductionmentioning

confidence: 99%

Solvent Perturbation of the Electronic Intensity of Solvated Absorbing Molecules

Ahmed¹,

Obi-Egbedi²,

Iweibo³

2012

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In this paper, we present a general expression originating from quantum-mechanical perturbation treatment of electronic intensities and Hamiltonian operators for the system (H A and H B ) of an absorber and a perturber respectively. The expression is related to the Longuet-Higgins' definition of solute-solvent interaction and fitted into linear regression mode for the determination of transition polarizabilities of 9H-xanthene, 9H-xathone and 9H-xanthione. The result conforms to those earlier obtained when all possible interaction modes are considered.

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Solvent effects on the intensities of the weak ultraviolet spectra of ketones and nitroparaffins—I

Cited by 86 publications

References 8 publications

Some applications of the direct reaction field approach

Some applications of the direct reaction field approach

Solvent-Induced Frequency Shifts: Configuration Interaction Singles Combined with the Effective Fragment Potential Method

Solvent Perturbation of the Electronic Intensity of Solvated Absorbing Molecules

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