spectroscopy using molecular dynamics: theory and application to CH5+ and its isotopologues
Computing and assigning infrared spectra via molecular dynamics is a powerful technique to unravel the structure and dynamics of molecular systems of ever increasing complexity.
Electronic structure analysis of multistate reactivity in transition metal catalyzed reactions: the case of C–H bond
activation by non-heme iron(IV)– oxo cores
This perspective discusses the principles of the multistate scenario often encountered in transition metal catalyzed reactions. To this end, the reaction of C–H bond activation by non-heme FeIVoxo intermediates is taken as an example to show how to gain chemical insights from the electronic structure analysis.
Comparing molecular photofragmentation dynamics in the gas and liquid phases
This perspective explores the extent to which the early time dynamics of molecular photofragmentation processes in solution mimic behaviour observed in the gas phase.
Rotational spectroscopy meets theory
Overview of the quantum-chemical calculation of rotational spectroscopy parameters: the support of theory in supporting experiment is detailed.
Modeling environment effects on spectroscopies through QM/classical models
An overview of potentials and limits of hybrid QM/classical approaches to simulate spectroscopies of molecules in environments of increasing complexity.
The chemical sensitivity of
X-ray spectroscopy: high energy resolution XANES versus X-ray emission spectroscopy of substituted ferrocenes
The limits of the chemical sensitivity of X-ray spectroscopy are explored using a combination of experiment and theory.
Investigation by two-color IR dissociation
spectroscopy of Hoogsteen-type binding in a metalated nucleobase pair mimic
IR-MPD spectroscopy by a novel two color scheme proved self-assembly of a metalated nucleobase pair mimic by Hoogsteen binding.
The electronic structure of pyracene: a spectroscopic and computational study
The electronic structure of pyracene has been investigated by spectroscopy and quantum chemistry.
Intrinsic fluorescence properties of rhodamine cations in gas-phase: triplet lifetimes and dispersed fluorescence spectra
Intersystem crossing from the triplet manifold to the ground state is studied in the gas phase for several rhodamine cations. Gas phase triplet lifetimes on the order of seconds, dispersed fluorescence measurements at cryogenic temperature, as well as B3LYP calculations are reported.
spectroscopy: effects of higher excited electronic states
The present paper is devoted to the simulation of (integral and dispersed) pump–probe signals in the nonperturbative regime for a series of material systems with multiple electronic states and excited-state absorption.
Electron tunneling from electronically excited states of isolated bisdisulizole-derived trianion
chromophores following UV absorption
Time-resolved photoelectron spectroscopy of Bisdisulizole-derived trianions shows ESETD.
Rovibrational states of ClHCl− isotopologues up to high J: a joint theoretical and spectroscopic investigation
Explicitly correlated coupled cluster calculations help with the assignment of diode laser IR spectra of ClHCl− isotopologues and enable the analysis of subtle rovibrational interactions.
Azidoacetylene – interpretation of gas phase infrared spectra based on high-level vibrational configuration interaction calculations
The vibrational spectrum of azidoacetylene, being dominated by strong Fermi resonances and intense overtones, has been analyzed by vibrational configuration interaction calculations.
Specific many-electron effects in
X-ray spectra of simple metals and graphene
K and L edge X-ray emission spectra of simple metals are calculated including dynamical core-hole screening in the valence band.
Non-bonding interactions and internal dynamics in CH2F2⋯H2CO: a rotational and model calculations study
The non-bonding interactions and the internal dynamics of CH2F2–CH2O are described interpreting the rotational features with appropriate theoretical models.
On the role of singlet versus triplet excited states in the uncaging of ortho-nitrobenzyl caged compounds
ortho-Nitrobenzylacetate (oNBA) is one of the smallest caged-compounds utilizing the famous ortho-nitrobenzyl caging group and thus serves here as a proto-typical example.
NMR through secular approximation
An alternate interpretation of the secular approximation is presented for describing and understanding the nuances of multi-quantum (MQ) NMR spectroscopy of quadrupolar nuclei.
Potential energy surfaces for ground and excited electronic states of the CF3I molecule and their relevance to its A-band photodissociation
Potential energy surfaces for the A-band states of CF3I are obtained in the multireference spin–orbit CI calculations and analyzed in relation to the CF3I photodissociation process.
Ab initio simulations of scanning-tunneling-
microscope images with embedding techniques and application to C58-dimers on Au(111)
An efficient method to simulate STM-images of large molecules is presented, which utilizes the embedding technique merged with standard quantum chemistry calculations.
In situ determination of the surface excess upon electrochemical sulfate
adsorption on Au(111) films by surface plasmon resonance
We have studied sulfate adsorption and desorption processes on gold surfaces, employing time resolved surface plasmon generation.
Ultrafast photoinduced dynamics of halogenated cyclopentadienes: observation of geminate charge-transfer complexes in solution
Photoexcited halogenated cyclopentadienes dissociate into radicals within <100 fs, which form highly stabilized geminate charge-transfer complexes depending on the solvent.
vibrational spectra from ab initio molecular dynamics
The computation of vibrational spectra from ab initio molecular dynamics simulations via time-correlation functions is presented and compared to static calculations within the harmonic approximation. Furthermore, the applicability to bulk phase systems is demonstrated.
QM/MM simulations of
vibrational spectra of bacteriorhodopsin and channelrhodopsin-2
A new model for an important structural motif of channelrhodopsin-2 is presented, which agrees well with simulations and experiments.
Spectroscopic and theoretical investigations of
adenosine 5′-diphosphate and adenosine 5′-triphosphate dianions in the gas phase
The interplay between repulsive negative charge density and attractive hydrogen bonds governs structure of dianionic ATP and ADP.
Computational study of the spin-state energies and
UV-Vis spectra of bis(1,4,7-triazacyclononane) complexes of some first-row transition metal cations
Ligand-field DFT versus Time-Dependent DFT on transition-metal cyclononane complexes, which one works better?
Benchmarks for 0–0 transitions of aromatic organic molecules: DFT/B3LYP, ADC(2), CC2, SOS-CC2 and SCS-CC2 compared to high-resolution gas-phase data
A new test set for 0–0 transition energies in organic molecules, consisting of 66 electronic origins taken from high-resolution measurements in supersonic jets, has been compiled and evaluated for second-order wave function methods and DFT/B3LYP.
About this collection
This is the official themed issue of the international Bunsentagung 2013 meeting on the same theme organised by the Deutsche Bunsen-Gesellschaft (DBG) which took place from May 9-11, 2013 in Karlsruhe, Germany. The issue was Guest Edited by Manfred Kappes and Wim Klopper.