We combine ultrafast electronic and vibrational spectroscopy and computational modeling to investigate the photoinduced excited-state intramolecular hydrogen-transfer dynamics in 1,8-dihydroxy-9,10-anthraquinone (DHAQ) in tetrachloroethene, acetonitrile, dimethyl sulfoxide, and methanol. We analyze the electronic excited states of DHAQ with various possible hydrogen-bonding schemes and provide ...

Using angle-resolved photoemission and linearly polarized synchrotron radiation, we measured the electronic band structure of electronic states of CuO2 plane materials ranging from insulators ~Sr2CuO2Cl2) to overdoped superconductors ~Bi2Sr2CaCu2O81x). We report three results: ~i! The CuO2 containing insulator possesses a spin-density-wave ~SDW! ground state; ~ii! there are precursors of the SD...

A simple derivation of the general equations of the Tamm-Dankoff approximation (TDA) is presented using the equation-of-motion technique to describe electronic excitations in molecules. It is emphasized that the performance of this method strongly depends on the accuracy of the reference (ground) state. Though the HartreeFock ground state is commonly applied, the 'all-single CI' (CIS) method ba...

The penta-2,4-dieniminium cation (PSB3) displays similar ground state and first excited state potential energy features as those of the retinal protonated Schiff base (RPSB) chromophore in rhodopsin. Recently, PSB3 has been used to benchmark several electronic structure methods, including highly correlated multireference wave function approaches, highlighting the necessity to accurately describ...

Making use of self-assembly techniques, we realize nanoscopic semiconductor quantum rings in which the electronic states are in the true quantum limit. We employ two complementary spectroscopic techniques to investigate both the ground states and the excitations of these rings. Applying a magnetic field perpendicular to the plane of the rings, we find that, when approximately one flux quantum t...

Femtosecond broadband transient absorption spectroscopy has been used in a comparative study of the ultrafast photo-induced Z → E isomerisation reactions of four photochromic furylfulgides with selected structural motifs in n-hexane as solvent. The results show that all studied Z-fulgides exhibit fast and direct processes along barrierless excited-state pathways involving a conical intersection...

There have been a number of recent experimental investigations of the nonadiabatic relaxation dynamics of aniline following excitation to the first three singlet excited states, 1(1)ππ*, 1(1)π3s/πσ* and 2(1)ππ*. Motivated by differences between the interpretations of experimental observations, we have employed CASSCF and XMCQDPT2 calculations to explore the potential energy landscape and relaxa...

The electronic state orderings and energies of heteroaryl oxenium ions were computed using high-level CASPT2//CASSCF computations. We find that these ions have a number of diverse, low-energy configurations. Depending on the nature of the heteroaryl substituent, the lowest-energy configuration may be open-shell singlet, closed-shell singlet, or triplet, with further diversity found among the su...