Molecular Theory of Solvent Effect on Keto−Enol Tautomers of Formamide in Aprotic Solvents:  RISM-SCF Approach

Ishida, Tateki; Hirata, Fumio; Sato, Hirofumi; Kato, Shigekí

doi:10.1021/jp973137t

Cited by 15 publications

(19 citation statements)

References 40 publications

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“…However, the predicted transition energy is in good agreement with the available experimental data. One reason for this may be that the experimental spectrum was measured in acetonitrile, where the formamide−solvent hydrogen bond is relatively weak . Experimental work on similar amides suggests that the nπ* state does undergo a blue shift in water.…”

Section: Resultsmentioning

confidence: 99%

“…The tautomerization of formamide is an example in which the inclusion of an explicit solvent molecule can provide additional theoretical insight into a reaction. Bulk solvent is found to stabilize the keto tautomer relative to the enol form because of the higher dipole moment of formamide. , However, studies that included explicit solvent molecules have shown that this trend can be offset by the formation of stronger hydrogen bonds in the enol form. , In addition, the reaction mechanism changes to a solvent-assisted scheme, lowering the activation energy. ,− …”

Section: Introductionmentioning

confidence: 99%

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Ab Initio Study of the Electronic Spectrum of Formamide with Explicit Solvent

Besley

Hirst

1999

J. Am. Chem. Soc.

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Of the many roles that solvent plays, its influence on molecular electronic structure is perhaps one of the more challenging phenomena to study. In this study, the effect of solvation on the electronic spectrum of formamide is investigated. Ab initio complete-active-space self-consistent field (CASSCF) and multiconfigurational second-order perturbation theory (CASPT2) methods are used to compute the ground- and excited-state energies of formamide complexed with one, two, and three water molecules. In addition, a semicontinuum approach is employed, in which formamide−(H2O) n (n = 1, 3) complexes are studied within a continuum solvent model. The presence of the explicit water molecules destabilizes the Rydberg states of formamide by approximately 0.5 eV. In the case of the πnbπ* transition, a red shift from 7.41 eV (gas phase) to 7.16 eV is observed, and its oscillator strength increases by ∼10%. The nπ* transition undergoes a blue shift which is dependent on the O- - -H formamide−water hydrogen bond distance. The physical origin of these solvatochromic shifts is investigated. The former effects have been well reproduced in a previous ab initio study with a continuum model. In contrast, at least one explicit water molecule is needed to observe the blue shift in the nπ* transition. The semicontinuum approach provides a description of the electronic spectrum of solvated formamide that captures important local and bulk solvent effects.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Ab Initio Study of the Electronic Spectrum of Formamide with Explicit Solvent

Besley

Hirst

1999

J. Am. Chem. Soc.

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“…On a side note, substituted 2-thiazolinones/2-hydroxythiazoles are subject to acid-catalyzed ring mutation reactions [51,52,53]. Concerns about the possible sensitivity of 5-thiazolinones/5-hydroxythiazoles 10 / 4 to analogous isomerization processes were rapidly allayed by the observation that all such compounds remained unchanged upon storage for several weeks at low temperature.…”

Section: Resultsmentioning

confidence: 99%

Catalyst-Free Synthesis of Polysubstituted 5-Acylamino-1,3-Thiazoles via Hantzsch Cyclization of α-Chloroglycinates

et al. 2019

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“…Ishida et al carried out RISM-SCF computations of the energy difference in various solvents, including carbon tetrachloride (CCl 4 ), carbon disulfide (CS 2 ), dimethyl ether (DME), tetrahydrofuran (THF), acetonitrile (CH 3 CN), and dimethyl sulfoxide (DMSO). 121 The keto-enol tautomerization of acetylacetone is interesting, because the equilibrium is governed by the surrounding solvent. While the enol form is stable in the gas phase and in nonpolar solvent, the keto form is dominative in a polar environment.…”

Section: Chemical Equilibrium and Molecular Structurementioning

confidence: 99%

A modern solvation theory: quantum chemistry and statistical chemistry

Sato

2013

Phys. Chem. Chem. Phys.

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This perspective highlights recent developments in the field of statistical mechanics for molecular liquids, i.e. the integral equation (IE) theory, especially focusing on hybrid approaches incorporating quantum chemistry and IE theory. The electronic structure of solvated molecules is characterized, followed by recent developments and applications. The latter includes for some specific systems: evaluation of acidity, basicity, pH and pKa, chemical equilibrium and molecular structure, chemical reactions, ionization and electron transfer reactions, as well as excited states and their free energy.

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Molecular Theory of Solvent Effect on Keto−Enol Tautomers of Formamide in Aprotic Solvents: RISM-SCF Approach

Cited by 15 publications

References 40 publications

Ab Initio Study of the Electronic Spectrum of Formamide with Explicit Solvent

Ab Initio Study of the Electronic Spectrum of Formamide with Explicit Solvent

Catalyst-Free Synthesis of Polysubstituted 5-Acylamino-1,3-Thiazoles via Hantzsch Cyclization of α-Chloroglycinates

A modern solvation theory: quantum chemistry and statistical chemistry

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