We show that the transition origins of electronic excitations identified by quantified natural transition orbital (QNTO) analysis can be employed to connect potential energy surfaces (PESs) according to their character across a widerange of molecular
geometries. This is achieved by locating the switching of transition origins of adiabatic potential surfaces as the geometry changes. The transition vectors for analysing transition origins are provided by linear response time-dependent density functional theory (TDDFT) calculations under the Tamm-Dancoff approximation. We study the photochemical CO ring opening of oxirane as an example and show that the results corroborate the traditional Gomer-Noyes mechanism derived experimentally. The knowledge of specific states for the reaction also agrees well with that given by previous theoretical work using TDDFT surface-hopping dynamics that was validated by high-quality quantum Monte Carlo calculations. We also show that QNTO can be useful for considerably larger and more complex systems: by projecting the excitations to those of a reference oxirane molecule, the approach is able to identify and analyse specific excitations of a trans-2,3-diphenyloxirane molecule.
We systematically investigate the possible complex transition origin of electronic excitations of giant molecular systems by using the recently proposed QNTO analysis [J.-H. Li, J.-D. Chai, G. Y. Guo and M. Hayashi, Chem. Phys. Lett., 2011, 514, 362.
] combined with long-range corrected TDDFT calculations. Thymine (Thy) related excitations of biomolecule B-DNA are then studied as examples, where the model systems have been constructed extracting from the perfect or a X-ray crystal (PDB code 3BSE) B-DNA structure with at least one Thy included. In the first part, we consider the systems composed of a core molecular segment (e.g. Thy, di-Thy) and a surrounding physical/chemical environment of interest (e.g. backbone, adjacent stacking nucleobases) and examine how the excitation properties of the core vary in response to the environment. We find that the orbitals contributed from DNA backbone and surrounding nucleobases often participate in a transition of Thy-related excitations affecting their composition, absorption energy, and oscillator strength. In the second part, we take into account geometrically induced variation of the excitation properties of various B-DNA segments, e.g. di-Thy, dTpdT etc., obtained from different sources (ideal and 3BSE). It is found that the transition origin of several Thy-related excitations of these segments is sensitive to slight conformational variations, suggesting that DNA with thermal motions in cells may from time to time exhibit very different photo-induced physical and/or chemical processes.
We show that the origin of electronic transitions of molecular many-body systems can be revealed by a quantified natural transition orbitals (QNTO) analysis and the electronic excitations of the total system can be mapped onto a standard orbitals set
of a reference system. We further illustrate QNTO on molecular systems by studying the origin of electronic transitions of DNA moiety, thymine and thymidine. This QNTO analysis also allows us to assess the performance of various functionals used in time-dependent density functional response theory.
Improved wavelength calibrators for high-resolution astrophysical spectrographs will be essential for precision radial velocity (RV) detection of Earth-like exoplanets and direct observation of cosmological deceleration. The astro-comb is a combinati
on of an octave-spanning femtosecond laser frequency comb and a Fabry-Perot cavity used to achieve calibrator line spacings that can be resolved by an astrophysical spectrograph. Systematic spectral shifts associated with the cavity can be 0.1-1 MHz, corresponding to RV errors of 10-100 cm/s, due to the dispersive properties of the cavity mirrors over broad spectral widths. Although these systematic shifts are very stable, their correction is crucial to high accuracy astrophysical spectroscopy. Here, we demonstrate an emph{in-situ} technique to determine the systematic shifts of astro-comb lines due to finite Fabry-Perot cavity dispersion. The technique is practical for implementation at a telescope-based spectrograph to enable wavelength calibration accuracy better than 10 cm/s.
