Microwave spectroscopic study of malonaldehyde. 3. Vibration-rotation interaction and one-dimensional model for proton tunneling

Baughcum, Steven L.; Smith, Zuzana; Wilson, Edwin Bidwell; Duerst, Richard W.

doi:10.1021/ja00320a007

Cited by 232 publications

(130 citation statements)

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“…Experimentally, this barrier is estimated to be of the order of 4.0-5.2 kcal/mol. 68 Barone and Adamo 7 have studied the dependence of the proton transfer barrier upon the basis set and the correlation technique. They showed that the better agreement with experiment was obtained by CCSD(T)/DZP calculations.…”

Section: Methodsmentioning

confidence: 99%

How Malonaldehyde Bonds Change during Proton Transfer

et al. 1998

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The proton transfer mechanism in malonaldehyde has been investigated from the points of view of the topological analysis of the electron localization function and of the catastrophe theory. The calculations were carried out at the B3LYP hybrid functional level with the ccp-VTZ basis set. Complementary calculations were performed at the HF, MP2, BLYP, and B3LYP levels with the STO-3G, 6-31G, and 6-31G** basis sets in order to discuss the stability of the method. The mechanism of the reaction does not involve any reorganization of the skeleton: it is localized in the hydrogen bond region and involves three chemical structures corresponding to the reactant, the transition state, and the product. It is shown that the proton detachment is in fact the covalent breaking of the OH bond, and by symmetry its attachment on the other oxygen is also a covalent process. The analysis of the catastrophe shows that the reaction is driven by two active coordinates related to the OH and OO distance and provides a method for the determination of the limiting paths.

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Section: Methodsmentioning

confidence: 99%

How Malonaldehyde Bonds Change during Proton Transfer

et al. 1998

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“…Early experimental investigations on the tunneling splitting [1][2][3][4] on MA sparked a series of theoretical studies aiming to understand the nature of its ground vibrational state. The early theoretical works of Carrington and Miller 5,6 have shown that a one-dimensional effective treatment of the proton tunneling on MA is fundamentally flawed.…”

Section: Introductionmentioning

confidence: 99%

The ground state tunneling splitting of malonaldehyde: Accurate full dimensional quantum dynamics calculations

Coutinho-Neto

Viel

Manthe

2004

The Journal of Chemical Physics

122

102

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Benchmark calculations of the tunneling splitting in malonaldehyde using the full dimensional potential proposed by Yagi et al. [J. Chem. Phys. 115, 10647 (2001)] are reported. Two exact quantum dynamics methods are used: the multiconfigurational time-dependent Hartree (MCTDH) approach and the diffusion Monte Carlo based projection operator imaginary time spectral evolution (POITSE) method. A ground state tunneling splitting of 25.7±0.3 cm−1 is calculated using POITSE. The MCTDH computation yields 25 cm−1 converged to about 10% accuracy. These rigorous results are used to evaluate the accuracy of approximate dynamical approaches, e.g., the instanton theory.

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“…In 1976 Wilson's group published the first of several [9][10][11][12] studies on the microwave spectroscopy of the C, H, and O isotopomers of MA. These established its internally H bonded geometry, equal double-minimum nature of the PES, and coherent quantum tunneling activity.…”

Section: Coherent Tunneling Splitting Phenomena In Malonaldehydementioning

confidence: 99%

“…MA has 21 and TRN has 39 internal coordinates available for coupling into their tunneling processes. MA, with a developing experimental base [9][10][11][12][13][14][15][16][17][18][19][20][21], holds a computational edge over TRN which currently stands alone in its size group for its catalog of spectroscopic tunneling structures [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39]. With 15 atoms TRN is reasonably expected to model elements of the intramolecular dynamical behavior occurring in much larger molecules, and it is amenable to high level experimental and theoretical studies.…”

Section: Introductionmentioning

confidence: 99%

Coherent Proton Tunneling in Hydrogen Bonds of Isolated Molecules: Malonaldehyde and Tropolone

Redington

2006

Hydrogen‐Transfer Reactions

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A series of articles reporting temperature dependent H and D isotope effects on the rates of certain enzymatic H transfer reactions show there is quantum tunneling by the H in these systems [1][2][3][4][5][6][7]. Theoretical considerations [4,6,7] infer vibrations within the enzyme-substrate complex, especially within the enzyme protein, develop transient geometrical configurations fomenting the tunneling process. Details of the promoting vibrations are still speculative, but it seems clear they work through transient reshaping of the potential energy surface (PES) barrier region, its width, energy maximum, overall contour, to provide "gated" impetus to H tunneling and to product escape.Molecules hosting coherent H tunneling activity in the presence of complex vibrational structure are of immediate interest in the above context. They provide sharp data points probing specific vibrational couplings along the large amplitude tunneling coordinate, and they probe portions of the PES topography in detail. Studies on isotopomers and close chemical congeners provide clusters of data points reflecting systematic changes of the dynamical behavior. In this chapter research on the coherent tunneling properties of malonaldehyde, tropolone, and tropolone derivatives is surveyed. These are among the few currently known 10-15 atom molecules showing clear-cut spectral doublet structures signifying coherent tunneling properties. Interestingly, the equal double-minimum global PESs for these molecules, notably for S 0 tropolone, are also poised for demonstrations of tunneling activity by the heavy atoms. The presence of H tunneling in some enzymatic systems is newly recognized; tunneling processes by heavy atoms such as C, N, and O may also prove consequential. Zuev et al. [8] recently published low temperature rate data and theoretical-computational results showing the tunneling of C atom from a single quantum state during the ring expansion isomerization of 1-methycyclobutylfluorocarbene.

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Microwave spectroscopic study of malonaldehyde. 3. Vibration-rotation interaction and one-dimensional model for proton tunneling

Cited by 232 publications

References 0 publications

How Malonaldehyde Bonds Change during Proton Transfer

How Malonaldehyde Bonds Change during Proton Transfer

The ground state tunneling splitting of malonaldehyde: Accurate full dimensional quantum dynamics calculations

Coherent Proton Tunneling in Hydrogen Bonds of Isolated Molecules: Malonaldehyde and Tropolone

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