Molecular Spectra, Reaction Dynamics, Symmetries and Life

Abstract

We provide a short review of the work of the group for molecular kinetics and spectroscopy at the Laboratory for Physical Chemistry of ETH Zürich contributing to our understanding of the fundamental physical-chemical primary processes in chemical reactions. After a brief historical introduction, we present a selection of recent progress and thinking in three areas: 1. Experiments in high resolution molecular spectroscopy leading us from an elucidation and unraveling of molecular infrared spectra to the understanding of the molecular reaction dynamics and fast intramolecular processes from the nanosecond (1 ns = 10 -9 s) to the femtosecond (1 fs = 10 -15 s) and even sub-fs or attosecond (1 as = 10 -18 s) domain. 2. Theory of fundamental symmetries of physics and their violations in molecular spectra and dynamics of chiral molecules with a discussion of possible consequences for the role of chirality in the origin of life. 3. Speculative considerations on the relationship of spectra and dynamics of chiral molecules with the CPT theorem of physics and with the origin of matter and chiral life, and on the relationship of time reversal symmetry violation with the molecular origin of irreversibility and with the possible molecular origin of thought.

Survey of the high resolution infrared spectrum of methane (12CH4 and 13CH4): Partial vibrational assignment extended towards 12 000 cm−1

“…Using the strategy 39,40,[80][81][82] of the direct assignment of the J = 0 levels of excited vibrational states of F 2 symmetry in low temperature spectra of 12 CH 4 and 13 CH 4 we have been able in the present work to extend the accurate knowledge for a considerable number of the vibrational level energies for these methane isotopomers up to 12 000 cm −1 (about 20 levels in a range where few previous data existed 80,82,119,132 ). We have furthermore extended the theoretical formulation for the effective Hamiltonian for the T d symmetrical isotopomers of methane to cover excitations up to this range.…”

High‐Resolution Fourier Transform Infrared Spectroscopy

“…High-resolution analyses of the IR spectra of chiral molecules are still very scarce. They provide a necessary first step toward further experiments designed for detecting molecular parity violation as discussed in Quack (1986Quack ( , 1989bQuack ( , 2002, Daussy et al (1999), Laerdahl et al (2000), Hollenstein et al (1997), Quack and Stohner (2000, 2003, Gross et al (1998), Quack and Willeke (2006), Berger and Quack (2000a,b). This kind of effort provides a connection between molecular spectroscopy and fundamental high-energy physics.…”

“…The availability of these instruments led to early developments in Doppler-limited high-resolution FTIR-supersonic jet techniques , Amrein et al 1987a,b, 1988a) (see review (Quack 1990) and Snels et al 2011: High-resolution FTIR and Diode Laser Spectroscopy of Supersonic Jets, for further references). It also contributed importantly to the high-resolution spectroscopic approach to short-time (as-fs-ps) intramolecular quantum dynamics and kinetics (Marquardt and Quack 2001, Quack 1990, 2001, 2003: Fundamentals of Rotation-Vibration Spectra, this handbook).…”

Mode-selective stereomutation tunneling and parity violation in HOClH+ and H2Te2 isotopomers

“…The recent theoretical discovery that E pv is predicted to be one to two orders of magnitude larger [21][22][23][24] than anticipated from earlier calculations [18] has given new impetus to the field and the present work contributes to the new effort in this field [19][20][21][22][23][24][25][26][27][28][29][30][31][32][33]. From both an experimental and theoretical point of view, it would be of interest to study particularly simple prototype molecules or ions.…”