Polarizable embedding QM/MM: the future gold standard for complex (bio)systems?
We provide a perspective of the induced dipole formulation of polarizable QM/MM, showing how efficient implementations will enable their application to the modeling of dynamics, spectroscopy, and reactivity in complex biosystems.
Cold and controlled chemical reaction dynamics
State-to-state chemical reaction dynamics, with complete control over the reaction parameters, offers unparalleled insight into fundamental reactivity.
How nature covers its bases
The response of nucleobases to UV radiation depends on structure in subtle ways, as revealed by gas-phase experiments.
Differentiation of peptide isomers by excited-state photodissociation and ion–molecule interactions
Solvatochromic effects reveal isomer identity in the gas phase.
Local dynamics of the photo-switchable protein PYP in ground and signalling state probed by 2D-IR spectroscopy of –SCN labels
We employ 2D-IR spectroscopy of the protein label –SCN to describe the local dynamics in the photo-switchable protein PYP in its dark state (pG) and after photoactivation, concomitant with vast structural rearrangements, in its signalling state (pB).
Benchmarking a new segmented K-band chirped-pulse microwave spectrometer and its application to the conformationally rich amino alcohol isoleucinol
Isoleucinol, a potential precursor to the essential α-amino acid isoleucine, has been studied using microwave spectroscopy from 2–26 GHz, with the measurements between 18–26 GHz taking place on a newly designed spectrometer.
Electric-field-mediated magnetic properties of all-oxide CoFe2O4/La0.67Sr0.33MnO3/Pb(Mg1/3Nb2/3)0.7Ti0.3O3 heterostructures
The coercivity of the CFO/LSMO/PMN-PT heterostructures decreases ∼50%, making it possible to achieve electric-field-controlled magnetoresistance.
On the polarization of ligands by proteins
The ligand polarization energy is evaluated for 286 crystallographic complexes from the PDBBind Core Set. It is found to be a substantial and variable highly fraction of the total protein–ligand interaction energy.
How do mutations affect the structural characteristics and substrate binding of CYP21A2? An investigation by molecular dynamics simulations
CYP21A2 mutations affect the activity of the protein leading to CAH disease.
Synergies and compromises between charge and energy transfers in three-component organic solar cells
In a three-component OSC, proper interface design is crucial to reaching the right balance between charge and energy transfer when both processes occur. Highly transparent devices can be built by thinning the active layer without affecting the PCE.
Are 2D fingerprints still valuable for drug discovery?
Recently, low-dimensional mathematical representations have overshadowed other methods in drug discovery. This work reassesses eight 2D fingerprints on 23 molecular datasets and reveals that they can perform as well as mathematical representations in tasks involving only small molecules.
Electric control of magnetization in an amorphous Co–Fe–Ta–B–O film by resistive switching
A reversible and nonvolatile control of magnetization was achieved in a Co–Fe–Ta–B–O film at room temperature by resistive switching.
Time-resolved formation of excited atomic and molecular states in XUV-induced nanoplasmas in ammonia clusters
The formation of excited hydrogen in XUV-induced ammonia plasmas was studied in a time-resolved way using an XUV-UV pump–probe scheme.
Impact of electronic polarizability on protein-functional group interactions
Interactions of proteins with functional groups are key to their biological functions, making it essential that they be accurately modeled.
Electric-field control of single-molecule tautomerization
The combination of a graphene field-effect transistor and a gate-tunable scanning tunneling microscope enables independent control over the electric field. Using this method, we studied the electric field effect on the tautomerization reaction.
State-to-state photodissociation dynamics of CO2 around 108 nm: the O(1S) atom channel
We report here the state-to-state photodissociation dynamical characteristics of the O(1S) + CO(X1Σ+) channel at a series of photolysis wavelengths from 107.37 to 108.84 nm.
Formation of highly excited iodine atoms from multiphoton excitation of CH3I
Multiphoto-fragmentation (i.e. photodissociation and photoionization) processes for CH3I determined by slice imaging and mass resolved multiphoton ionization (MR-MPI).
Laser-induced alignment dynamics of gas phase CS2 dimers
Rotational dynamics of gas phase carbon disulfide (CS2) dimers were induced by a moderately intense, circularly polarized alignment laser pulse and measured as a function of time by Coulomb explosion imaging with an intense fs probe pulse.
Photoelectron spectroscopy of boron-containing reactive intermediates using synchrotron radiation: BH2, BH, and BF
Mass selected slow photoelectron spectra (SPES) of three boron-containing reactive species, BH2, BH, and BF were recorded by double imaging photoion–photoelectron coincidence spectroscopy (i2PEPICO) using synchrotron radiation.
Understanding the structure and dynamics of cationic surfactants from studies of pure solid phases
Unravelling the phase behaviour of n-alkyltrimethylammonium bromides (C10 to C18): from tight-packed interdigitation to rotational disorder with increasing temperature.
Considerable matrix shift in the electronic transitions of helium-solvated cesium dimer cation Cs2He+n
Small atom, large effects: solvation of cesium dimer cation, Cs2+, by helium leads to large shifts in the electronic spectrum.
Metadynamics for automatic sampling of quantum property manifolds: exploration of molecular biradicality landscapes
We present a general extension of the metadynamics allowing for an automatic sampling of quantum property manifolds (ASQPM) giving rise to functional landscapes. We illustrate our method on the example of biradical character in molecular systems.
A Bayesian approach to NMR crystal structure determination
We introduce a Bayesian framework for quantifying the reliability of structure determinations for powdered samples on the basis of NMR experiments and chemical shift predictions (with uncertainties) for a pool of candidate structures.
Enrichment of methanol inside pNIPAM gels in the cononsolvency-induced collapse
From Raman, we determined an enrichment of methanol inside the polymer in the cononsolvency-induced collapse and donor-type hydrogen-bonding of methanol with pNIPAM.
Elucidating the optical spectra of [Au25(SR)18]q nanoclusters
Density functional theory calculations reveal how optical spectra of [Au25(SR)18]q nanoclusters (q = −1, 0, +1) change with different ligands.
Beyond the Coulson–Fischer point: characterizing single excitation CI and TDDFT for excited states in single bond dissociations
HF/DFT orbitals spin-polarize when single bonds are stretched past the Coulson–Fischer point. We report unphysical features in the excited state potential energy surfaces predicted by CIS/TDDFT in this regime, and characterize their origin.
A coarse-grained model of ionic liquid crystals: the effect of stoichiometry on the stability of the ionic nematic phase
The thermal range of the ionic nematic phase is strongly influenced by the stoichiometric composition of the [GB]n[LJ]m salt in mixtures of Gay-Berne and Lennard-Jones charged-particles.
Asymptotic behavior of the Hartree-exchange and correlation potentials in ensemble density functional theory
We show that the Hartree-exchange and correlation potentials of ensemble systems can have unexpected features, including non-vanishing asymptotic constants and non-trivial screening of electrons. These features are demonstrated here on Li, C, and F.
Membrane softening by nonsteroidal anti-inflammatory drugs investigated by neutron spin echo
Incorporation of drugs makes membranes softer, and the magnitude of the effect depends on the drug and the phase of the membrane.
Multistate hybrid time-dependent density functional theory with surface hopping accurately captures ultrafast thymine photodeactivation
We report an efficient analytical implementation of first-order nonadiabatic derivative couplings between arbitrary Born–Oppenheimer states in the hybrid time-dependent density functional theory (TDDFT) framework using atom-centered basis functions.
The influence of support materials on the structural and electronic properties of gold nanoparticles – a DFT study
This study investigates the effect of commonly used support materials (MgO, C, CeO2) on small gold particles using dispersion corrected density functional theory (DFT-D).
Probing the structure of giant fullerenes by high resolution trapped ion mobility spectrometry
We present high-resolution trapped ion mobility spectrometry (TIMS) measurements for fullerene ions in molecular nitrogen.
Chemically-driven convective dissolution
Chemical reactions can trigger convection upon dissolution when the dissolving species reacts with a given solute in the host phase to create non-monotonic density profiles.
Surface anchored self-assembled reaction centre mimics as photoanodes consisting of a secondary electron donor, aluminium(III) porphyrin and TiO2 semiconductor
Vertically assembled photoanodes, consisting of aluminum(III) porphyrin, an electron donor, and semiconductor TiO2, have been fabricated and their photophysical properties investigated.
Identification of active sites in CO oxidation over a Pd/Al2O3 catalyst
The active sites of Pd/Al2O3 catalysts for CO oxidations were identified by investigating the dependence of CO oxidation activities on the surface structure and morphology of Pd nanoparticles.
Influence of polar co-solutes and salt on the hydration of lipid membranes
The influence of the co-solutes TMAO, urea, and NaCl on the hydration repulsion between lipid membranes is investigated in a combined experimental/simulation approach.
Conformation of alkali metal ion-calixarene complexes investigated by IR spectroscopy in the gas phase
The OH bands of M+·C4A shift to the red from K+ to Cs+, indicating reduction of conformer distortion.
Structural reconfigurations of nanosheet arrays in layered minerals caused by wave irradiation: desorption mechanism of Cs from nanosheet edges
In layered minerals typically available in soil, there exists a high concentration of nanosheet edge sites formed by overlap among two-dimensional (2D) nanosheets, which act as heavily adhesive Cs chemisorption sites.
Investigation on photocatalytic mechanism of graphitic SiC (g-SiC)/MoS2 van der Waals heterostructured photocatalysts for overall water splitting
Two-dimensional MoS2-based heterostructures have been given great attention due to their excellent properties.
It's not just the defects – a curved crystal study of H2O desorption from Ag
Spatially-resolved temperature-programmed desorption of H2O from curved Ag surfaces resolves the causes of structure sensitivity in binding energy.
fs–ps Exciton dynamics in a stretched tetraphenylsquaraine polymer
A squaraine polymer shows surprisingly fast light induced energy transfer between two different structural sections on the ps/fs time scale.
The water–carbon monoxide dimer: new infrared spectra, ab initio rovibrational energy level calculations, and an interesting in-termolecular mode
Bound state rovibrational energy level calculations using a high-level intermolecular potential surface are reported for H2O–CO and D2O–CO.
Expanding the range of binding energies and oxidizability of biologically relevant S–aromatic interactions: imidazolium and phenolate binding to sulfoxide and sulfone
Oxidation and protonation/deprotonation strongly impact intermolecular noncovalent interactions.
Mapping the intrinsic absorption properties and photodegradation pathways of the protonated and deprotonated forms of the sunscreen oxybenzone
Laser photodissociation experiments on gas-phase protonated and deprotonated oxybenzone reveal how the absorption properties and photodegradation products are significantly affected by pH.
Surface phase diagrams of La-based perovskites towards the O-rich limit from first principles
A DFT study of surface phase diagrams of La-based perovskites in equilibrium with oxygen gas.
Room temperature quantum coherence vs. electron transfer in a rhodanine derivative chromophore
Quantum coherence and their interplay with electronic transfer (ET) in organic-based materials for light harvesting rely on the solvent properties and temperature effects, as shown in the figure for the D2F complex (D–A push–pull chromophore) population inversion (left), and ET rates (right) for methanol in the strong coupling regime. ET rates are enhanced, at room temperature, by two orders of magnitude if compared to results obtained for toluene.
Spectroscopic diagnostic for the ring-size of carbohydrates in the gas phase: furanose and pyranose forms of GalNAc
Hexoses are sparingly found in nature in the furanose form (5-membered ring).
Triplet–triplet annihilation based photon up-conversion in hybrid molecule–semiconductor nanocrystal systems
Photon up-conversion based on triplet–triplet annihilation (TTA) in a hybrid system exploits the annihilation of optically dark triplets of an organic emitter, sensitized by a semiconductor nanocrystal, to produce high-energy singlets that generate high energy emission.
About this collection
Over the course of 2020, the Associate Editors of Physical Chemistry Chemical Physics have each chosen a handful of articles that they believe are of outstanding quality and deserve to be highlighted to the wider community through our Editor’s Choice collection. The breadth of the Editorial Board is demonstrated by the wide variety of topics showcased in this collection. All of these exceptional articles are collated here for you to enjoy.