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Themed collection Challenges in spectroscopy: accuracy vs interpretation from isolated molecules to condensed phases

36 items
Editorial

Challenges in spectroscopy: accuracy versus interpretation from isolated molecules to condensed phases

This themed issue includes a collection of articles on Challenges in spectroscopy: accuracy versus interpretation from isolated molecules to condensed phases.

Graphical abstract: Challenges in spectroscopy: accuracy versus interpretation from isolated molecules to condensed phases
Perspective

Quantum approaches to vibrational dynamics and spectroscopy: is ease of interpretation sacrificed as rigor increases?

The subject of this Perspective is quantum approaches, beyond the harmonic approximation, to vibrational dynamics and IR spectroscopy.

Graphical abstract: Quantum approaches to vibrational dynamics and spectroscopy: is ease of interpretation sacrificed as rigor increases?
Perspective

On the prediction of core level binding energies in molecules, surfaces and solids

Core level binding energies, measured by X-ray photoelectron spectroscopy providing unique information regarding the chemical environment of atoms in a system, can be estimated by a diversity of state-of-the-art accurate methods here detailed.

Graphical abstract: On the prediction of core level binding energies in molecules, surfaces and solids
Paper

New insights about the monomer and homodimer structures of the human AOX1

We conducted MD simulations to provide a comprehensive study on the human aldehyde oxidase and on the impact that the allosteric inhibitor thioridazine and malonate ions have on its structure, particularly on the catalytic tunnel.

Graphical abstract: New insights about the monomer and homodimer structures of the human AOX1
Open Access Paper

N2+(2Σg) and Rb(2S) in a hybrid trap: modeling ion losses from radiative association paths

N2+ + Rb → (N2Rb)+(v) + ħω radiative association: partial vibronic cross-sections corresponding to the R8 transition as a function of the emitted photon energies and wavelengths in the ultraviolet region.

Graphical abstract: N2+(2Σg) and Rb(2S) in a hybrid trap: modeling ion losses from radiative association paths
Paper

The role of dispersion and anharmonic corrections in conformational analysis of flexible molecules: the allyl group rotamerization of matrix isolated safrole

Conformational changes of the monomeric safrole isolated in low temperature xenon matrices, induced thermally or using narrow-band UV radiation, represent challenging example for the theoretical structural, spectroscopic and energetic analysis.

Graphical abstract: The role of dispersion and anharmonic corrections in conformational analysis of flexible molecules: the allyl group rotamerization of matrix isolated safrole
Paper

Accurate empirical rovibrational energies and transitions of H216O

Several significant improvements are proposed to the computational molecular spectroscopy protocol MARVEL (Measured Active Rotational–Vibrational Energy Levels), facilitating the inversion of a large set of measured rovibrational transitions to energy levels.

Graphical abstract: Accurate empirical rovibrational energies and transitions of H216O
Paper

Non covalent interactions stabilizing the chiral dimer of CH2ClF: a rotational study

Two C–H⋯Cl–C and one C–H⋯F–C bonds stabilize (by 5.9 kJ mol−1) the dimer of chlorofluoromethane observed by rotational spectroscopy in the gas phase. The spectral analysis is complicated by the quadrupolar effects of the two nonequivalent Cl nuclei.

Graphical abstract: Non covalent interactions stabilizing the chiral dimer of CH2ClF: a rotational study
Paper

Algebraic diagrammatic construction for the polarisation propagator in combination with effective fragment potentials

The effective fragment potential (EFP) method for the efficient inclusion of solvation effects is combined with the algebraic diagrammatic construction (ADC) scheme for the second- and third-order polarisation propagator.

Graphical abstract: Algebraic diagrammatic construction for the polarisation propagator in combination with effective fragment potentials
Paper

The Gigahertz and Terahertz spectrum of monodeutero-oxirane (c-C2H3DO)

The rotational spectrum of monodeutero-oxirane was analysed as measured using the Zurich Gigahertz (GHz) spectrometer and our highest resolution Fourier Transform Infrared (FTIR) spectrometer system coupled to synchrotron radiation at the Swiss Light Source (SLS).

Graphical abstract: The Gigahertz and Terahertz spectrum of monodeutero-oxirane (c-C2H3DO)
Paper

Rovibrational quantum dynamics of the vinyl radical and its deuterated isotopologues

Rotational–vibrational states up to 3200 cm−1, beyond the highest-lying stretching fundamental, are computed variationally for the vinyl radical (VR), H2Cβ[double bond, length as m-dash]CαH, and the following deuterated isotopologues of VR: CH2[double bond, length as m-dash]CD, CHD[double bond, length as m-dash]CH, and CD2[double bond, length as m-dash]CD.

Graphical abstract: Rovibrational quantum dynamics of the vinyl radical and its deuterated isotopologues
From the themed collection: 2018 PCCP HOT Articles
Paper

Internal dynamics of cyclohexanol and the cyclohexanol–water adduct

Two for a tango: the rotational spectrum of a cyclohexanol–water dimer evidences a concerted motion of the water molecule and the hydroxyl group of the ring.

Graphical abstract: Internal dynamics of cyclohexanol and the cyclohexanol–water adduct
Paper

Evaluating rotation diffusion properties of molecules from short trajectories

An efficient approach is reported to estimate the rotational diffusion tensor of molecules from the global angular momentum autocorrelation functions obtained from short molecular dynamics trajectories.

Graphical abstract: Evaluating rotation diffusion properties of molecules from short trajectories
Paper

The HKrCCH⋯CO2 complex: an ab initio and matrix-isolation study

Structure of the HKrCCH⋯CO2 complex prepared in a low-temperature krypton matrix.

Graphical abstract: The HKrCCH⋯CO2 complex: an ab initio and matrix-isolation study
Paper

A combined experimental and theoretical study of optical rotatory dispersion for (R)-glycidyl methyl ether in aqueous solution

We present a theoretical-experimental study of the optical rotation of (R)-glycidylmethylether using a mixed quantum-classical model for solvent effects.

Graphical abstract: A combined experimental and theoretical study of optical rotatory dispersion for (R)-glycidyl methyl ether in aqueous solution
Open Access Paper

Elucidating DNA binding of dithienylethenes from molecular dynamics and dichroism spectra

DNA intercalation and groove binding of two photoswitching dithienylethene derivatives have been studied and characterized by means of molecular dynamics and electronic circular dichroism.

Graphical abstract: Elucidating DNA binding of dithienylethenes from molecular dynamics and dichroism spectra
Paper

Far-IR and UV spectral signatures of controlled complexation and microhydration of the polycyclic aromatic hydrocarbon acenaphthene

UV and IR spectroscopic study of the controlled complexation and microhydration of a polycyclic aromatic hydrocarbon under isolated conditions using free electron laser FELIX.

Graphical abstract: Far-IR and UV spectral signatures of controlled complexation and microhydration of the polycyclic aromatic hydrocarbon acenaphthene
Paper

4s to 5s and 4p photoexcitation dynamics of K atoms from the surface of helium nanodroplets: a theoretical study

We study the photodissociation of the potassium atom from a superfluid helium nanodroplet upon 5s 2S or 4p 2P excitation using the time-dependent helium density functional method (He-TDDFT). The results show possible K spin–orbit relaxation.

Graphical abstract: 4s to 5s and 4p photoexcitation dynamics of K atoms from the surface of helium nanodroplets: a theoretical study
Paper

Unveiling anharmonic coupling by means of excited state ab initio dynamics: application to diarylethene photoreactivity

We adopted excited state ab initio dynamics and a new time resolved vibrational analysis to unveil coupling between modes promoting photorelaxation.

Graphical abstract: Unveiling anharmonic coupling by means of excited state ab initio dynamics: application to diarylethene photoreactivity
Paper

Molecular synthons for accurate structural determinations: the equilibrium geometry of 1-chloro-1-fluoroethene

The equilibrium structure for 1-chloro-1-fluoroethene is obtained by high-level quantum chemical calculations and the semi-experimental approach.

Graphical abstract: Molecular synthons for accurate structural determinations: the equilibrium geometry of 1-chloro-1-fluoroethene
Paper

Large amplitude vibrations of acetyl isocyanate, methyl cyanoformate, and acetyl cyanate

The far infrared region of three detectable molecules sharing the empirical formula C3H3O2N, acetyl isocyanate CH3CONCO (AISO), methyl cyanoformate NC–COOCH3 (MCN) and acetyl cyanate CH3COOCN (ACN), is explored using explicitly correlated coupled cluster ab initio methods and a variational procedure designed for non-rigid species and large amplitude motions.

Graphical abstract: Large amplitude vibrations of acetyl isocyanate, methyl cyanoformate, and acetyl cyanate
Paper

Aggregation of lactic acid in cold rare-gas matrices and the link to solution: a matrix isolation-vibrational circular dichroism study

Crucial insight into lactic acid self-aggregation in solution is obtained by following its unique VCD spectral features in cold matrices.

Graphical abstract: Aggregation of lactic acid in cold rare-gas matrices and the link to solution: a matrix isolation-vibrational circular dichroism study
Paper

The rotational spectrum of 15ND. Isotopic-independent Dunham-type analysis of the imidogen radical

First observation of the THz spectrum of 15ND. Global analysis of the imidogen radical spectra and derivation of the Born–Oppenheimer equilibrium bond length.

Graphical abstract: The rotational spectrum of 15ND. Isotopic-independent Dunham-type analysis of the imidogen radical
Paper

Pd doping, conformational, and charge effects on the dichroic response of a monolayer protected Au38(SR)24 nanocluster

TDDFT simulations of the absorption and CD spectra of a Pd2Au36(SC2H4Ph)24 monolayer-protected cluster (MPC) are carried out with the aim of investigating the effects of doping, conformational degrees of freedom of the thiolates’ end-groups, and charge states on its chiro-optical response.

Graphical abstract: Pd doping, conformational, and charge effects on the dichroic response of a monolayer protected Au38(SR)24 nanocluster
Paper

EPR sensing of metal and organic cations using a novel spin-labelled dibenzo-24-crown-8-ether

Novel dibenzo-24-crown ether substituted nitroxides and their use as spin probes for the detection of cation guests by EPR are reported.

Graphical abstract: EPR sensing of metal and organic cations using a novel spin-labelled dibenzo-24-crown-8-ether
Paper

Quantum tunneling dynamical behaviour on weakly bound complexes: the case of a CO2–N2 dimer

The dynamics induced by quantum tunneling is found to be closely connected to the shape of the potentials for weakly bound complexes.

Graphical abstract: Quantum tunneling dynamical behaviour on weakly bound complexes: the case of a CO2–N2 dimer
Paper

Theoretical insight into joint photodynamic action of a gold(I) complex and a BODIPY chromophore for singlet oxygen generation

Inclusion of a heavy gold atom in a peripheral position of BODIPY is enough to promote ISC.

Graphical abstract: Theoretical insight into joint photodynamic action of a gold(i) complex and a BODIPY chromophore for singlet oxygen generation
From the themed collection: 2018 PCCP HOT Articles
Paper

Double resonance rotational spectroscopy of He–HCO+

The ground state of He–HCO+ is investigated using a recently developed double resonance technique, consisting of a rotational transition followed by a vibrational transition into a dissociative state.

Graphical abstract: Double resonance rotational spectroscopy of He–HCO+
From the themed collection: 2018 PCCP HOT Articles
Paper

Interactions between azines and alcohols: a rotational study of pyridine–tert-butyl alcohol

The observed spectrum identifies a Cs symmetry σ-type complex, with the two subunits held together by coplanar “classical” O–H⋯N and weak C–H⋯π intermolecular hydrogen bonds. The O⋯N distance decreases by 4 mÅ upon deuteration of the hydroxyl group (reverse Ubbelohde effect).

Graphical abstract: Interactions between azines and alcohols: a rotational study of pyridine–tert-butyl alcohol
Paper

Computing vibration–rotation-tunnelling levels of HOD dimer

Using an accurate 6D water dimer potential energy surface, we compute vibration–rotation-tunnelling levels of HOD dimer, by assuming that the two monomers are rigid.

Graphical abstract: Computing vibration–rotation-tunnelling levels of HOD dimer
Paper

Evaluation of the aggregation process in a mixture of propofol and benzocaine

Aggregation of propofol and benzocaine was explored using mass-resolved laser spectroscopy and DFT calculations.

Graphical abstract: Evaluation of the aggregation process in a mixture of propofol and benzocaine
Paper

State-of-the-art computation of the rotational and IR spectra of the methyl-cyclopropyl cation: hints on its detection in space

A route toward the detection of the methyl-cyclopropenyl cation in space: a spectroscopic characterization by state-of-the-art computational approaches.

Graphical abstract: State-of-the-art computation of the rotational and IR spectra of the methyl-cyclopropyl cation: hints on its detection in space
Paper

Spectroscopy of a rotating hydrogen molecule in carbon nanotubes

Computing the energy levels of molecular hydrogen rotating in carbon nanotubes of increasing size.

Graphical abstract: Spectroscopy of a rotating hydrogen molecule in carbon nanotubes
From the themed collection: 2018 PCCP HOT Articles
Paper

On the simulation of vibrationally resolved electronic spectra of medium-size molecules: the case of styryl substituted BODIPYs

Vibronic spectra of two BODIPY derivatives were computed using both Time-Independent (TI) and Time-Dependent (TD) formalisms including solvent and temperature effects with several DFT functionals.

Graphical abstract: On the simulation of vibrationally resolved electronic spectra of medium-size molecules: the case of styryl substituted BODIPYs
Paper

How to treat C–F stretching vibrations? A vibrational CD study on chiral fluorinated molecules

Due to the poor prediction of harmonic frequencies, vibrational modes containing C–F stretching motions are often strongly misplaced by common hybrid functionals. Herein we show that M06-2X functional performs exceptionally good in these cases.

Graphical abstract: How to treat C–F stretching vibrations? A vibrational CD study on chiral fluorinated molecules
Paper

The rotation–vibration spectrum of methyl fluoride from first principles

State-of-the-art theoretical methods are used to investigate the rotation–vibration spectrum of methyl fluoride.

Graphical abstract: The rotation–vibration spectrum of methyl fluoride from first principles
36 items

About this collection

The special issue will be devoted to the latest research outcomes in the modelling of spectroscopic properties of chemical systems spanning from isolated molecules to condensed phases, with particular focus on accuracy and interpretative capabilities of computational methodologies and the interplay of experiment and theory. Indeed, in the last few years the interplay of quantum chemistry and experimental spectroscopy has strongly increased the dimension of systems amenable to an accurate characterization, thus extending to building blocks of biomolecules, condensed phases and flexible systems.

Guest Edited by Cristina Puzzarini (Università di Bologna), Maria J. Ramos (Universidade do Porto) and Maria Pilar de Lara-Castells (CSIC Madrid).

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