Proton transfer dynamics in the first excited singlet state of malonaldehyde

Abstract

Rotation-tunneling analysis of the origin band in the tropolone π*←π absorption system Semiclassical molecular dynamics simulations of excited state double-proton transfer in 7-azaindole dimers

Comparison of methods for calculating the properties of intramolecular hydrogen bonds. Excited state proton transfer

“…69 A smaller splitting in the 1 n* state, as compared to S o , [70][71][72] confirms the computational finding of a higher barrier in this excited state, ͑although later work questioned this interpretation͒. 73 Other experimental measurements are consistent with our computational finding that the 1 n* state of malonaldehyde is lower than 1 n*. 70,72 While there is no information on the asymmetric glyoxalmonohydrazine molecule itself, there are a number of studies of larger systems that contain the OH¯N intramolecular interaction within the context of one or more aromatic rings.…”

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

“…No evidence for the presence of resolved spectral tunneling doublets was reported by Firth et al [17] for Ar-isolated MA or by Chiavassa et al [18] Figure 1.2 Infrared spectrum of MA(OH) in the 200-300 cm -1 region due to Smith et al [15]. Spectral doublet separations DS 21 and DS 15 replace the single-peak assignments m 15 = peak 20 and m 21 = peak 26. in Ar, Kr, and Xe matrices. Smith et al [15] proposed a vibrational assignment for MA on the basis of their IR spectra for H and D isotopomers, comparative spectra for other substances, and a valence force field.…”

“…Seliskar and Hoffman [20] reported vibronic spectral structure for the weakà A 1 B 1 ‹X X 1 A 1 (p*-n) [S 1 ‹S 0 ] absorption near 354 nm to have a spectral doublet separation (DS) of 7 cm -1 . Arias et al [21] applied the absorbance-based degenerate four-wave mixing (DFWM) spectroscopic method to the S 1 ‹ S 0 transition. With higher intrinsic spectral resolution, and spectral clarification arising through the reduction of signal due to hot band transitions that is inherent in this nonlinear spectroscopic technique, they found DS = |D 0 S 1 -D 0 S 0 |~19 cm -1 , to place the ffi 1 [21].…”

“…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.…”

Time-resolved photoelectron spectroscopy of proton transfer in the ground state of chloromalonaldehyde: Wave-packet dynamics on effective potential surfaces of reduced dimensionality

“…[21][22][23][24][25][26] Most theoretical studies have focused on tunneling splitting in the ground state, [27][28][29][30][31][32][33][34][35][36][37] but proton transfer in electronically excited states has also been studied. [38][39][40][41][42][43][44] Spectroscopic studies of the real-time dynamics of proton transfer have been limited, to our knowledge, to excited electronic states. [45][46][47] In an application to o-hydroxybenzaldehyde and related compounds, Lochbrunner et al demonstrated the utility of pump-probe photoelectron spectroscopy for probing the dynamics of intramolecular proton transfer in excited states.…”