On the Statistical Regime, Coherence versus Incoherence and Ergodicity of Quantum Vibrational Trajectories in Soft Condensed Molecular Systems
Chemphyschem. 2024 Mar 22:e202300969. doi: 10.1002/cphc.202300969. Online ahead of print.ABSTRACTA theoretical-computational procedure, recently proposed for modelling Vibrational Energy Relaxation (VER) processes of a molecule (Quantum Center, QC) embedded in a complex atomic-molecular system, is extended and applied for analyzing in detail the features of the QC density matrix (DM) temporal evolution. The results, obtained using aqueous azide ion as a case study, show the total lack of coherence in the DM, when the system is prepared to be initially in a pure vibrational eigenstate. This finding is fully in line with the...
Source: Chemphyschem - March 22, 2024 Category: Chemistry Authors: Andrea Amadei Massimiliano Aschi Source Type: research
Cu(I) Coordination Compounds Conjugated to Au Nanorods for Future Applications in Drug Delivery: Insights in Molecular, Electronic and Cu Local Structure in Solid and Liquid Phase
Chemphyschem. 2024 Mar 22:e202400074. doi: 10.1002/cphc.202400074. Online ahead of print.ABSTRACTIn the framework of the design, synthesis and testing of a library of copper complexes and nanostructured assemblies potentially endowed with antitumor and antiviral activity and useful for several applications, from drugs and related delivery systems to the development of biocidal nanomaterials, we present the detailed spectroscopic investigation of the molecular and electronic structure of copper-based coordination compounds and of a new conjugated system obtained by grafting Cu(I) complexes to gold nanorods. More in detail, ...
Source: Chemphyschem - March 22, 2024 Category: Chemistry Authors: Alberto Lopez Simone Amatori Elena Olivieri Iole Venditti Giovanna Iucci Carlo Meneghini Federica Bertel à Fabio Del Bello Wilma Quaglia Maura Pellei Carlo Santini Chiara Battocchio Source Type: research
The Importance of Reaction Energy in Predicting Chemical Reaction Barriers with Machine Learning Models
Chemphyschem. 2024 Mar 22:e202300933. doi: 10.1002/cphc.202300933. Online ahead of print.NO ABSTRACTPMID:38517585 | DOI:10.1002/cphc.202300933 (Source: Chemphyschem)
Source: Chemphyschem - March 22, 2024 Category: Chemistry Authors: Nithin Lalith Aayush Singh Joseph A Gauthier Source Type: research
Co-solutes Induced Changes in the Properties of Polymeric Solution and Water Dynamics
Chemphyschem. 2024 Mar 22:e202400236. doi: 10.1002/cphc.202400236. Online ahead of print.ABSTRACTIn this paper we are addressing the co-solute-induced changes in the properties of an aqueous solution of a block copolymer. Due to the preferential interaction of different co-solute with different regions of the block copolymer, the changes were observed in both the physical properties and water dynamics. The modulation of both the physical properties and water dynamics was monitored using different spectroscopic techniques. Different co-solutes affect micellar properties of copolymer to a different extent signifying their in...
Source: Chemphyschem - March 22, 2024 Category: Chemistry Authors: Sanyukta Bhattacharjee Souvik Pandit Debabrata Seth Source Type: research
Surface Segregation Studies in Ternary Noble Metal Alloys: Comparing DFT and Machine Learning with Experimental Data
This study advances understanding of surface segregation and the utility of computational studies and highlights the need for further improvements in simulation accuracy.PMID:38517936 | DOI:10.1002/cphc.202400073 (Source: Chemphyschem)
Source: Chemphyschem - March 22, 2024 Category: Chemistry Authors: Kirby Broderick Robert Burnely Andrew J Gellman John Robert Kitchin Source Type: research
Tuning properties of layered materials based on hexagonal boron nitride by methylation: A density functional theory study
Chemphyschem. 2024 Mar 22:e202300882. doi: 10.1002/cphc.202300882. Online ahead of print.ABSTRACTIn this work, the rational design of optoelectronic properties of two-dimensional materials based on hexagonal boron nitride (h-BN) by functionalization by methyl (CH3) groups is proposed. Using density functional theory, we examine the functionalization of single- or double-layer systems with either CH3 radicals alone or with both CH3 (cations) and chlorine (anions), i.e., under conditions of homolytic or heterolytic splitting of CH3Cl precursor molecules, respectively. Different degrees of methylation (coverages) are consider...
Source: Chemphyschem - March 22, 2024 Category: Chemistry Authors: Elham Mazarei Peter Saalfrank Source Type: research
Effect of Surface Termination with Oxygen and Fluorine on the Electronic Structures and optical spectra of Mn2N Based MXenes
Chemphyschem. 2024 Mar 22:e202300605. doi: 10.1002/cphc.202300605. Online ahead of print.ABSTRACTThe extensive applications of MXenes, a novel type of layered materials known for their favorable characteristics, have sparked significant interest. This research focuses on investigating the impact of surface functionalization on the behavior of Mn2NX2 (X = O, F) MXenes monolayers using the "Density functional theory (DFT) based full-potential linearized augmented-plane-wave (FP-LAPW)" method. We observe and elucidate the variations in the physical properties of the Mn2NX2 by employing different surface terminations with F an...
Source: Chemphyschem - March 22, 2024 Category: Chemistry Authors: Bakhtiar Ul Haq Se-Hun Kim Aijaz Rasool Chaudhry S AlFaify Faheem K Butt S A Tahir R Ahmed A Laref Source Type: research
Infrared Laser Stark Spectroscopy of Methyl Fluoride in 4He Nanodroplets
The objective of performing Stark spectroscopy was to see if there is any evidence for a rotational linewidth dependence on the external field strength, due to a reduced difference in between methyl fluorides rotational energy gap and the roton-gap of superfluid helium. We did not find any evidence for such an effect, which we largely attribute to the rotational energy gap not increasing significantly enough by the external field. We point to another molecule (formaldehyde) whose energy levels are predicted to show a more promising response to application of an external field.PMID:38511250 | DOI:10.1002/cphc.202400224 (Source: Chemphyschem)
Source: Chemphyschem - March 21, 2024 Category: Chemistry Authors: Paul Raston Gary E Douberly Source Type: research
Advances in the Dynamics of Adsorbate Diffusion on Metal Surfaces: Focus on Hydrogen and Oxygen
Chemphyschem. 2024 Mar 21:e202400083. doi: 10.1002/cphc.202400083. Online ahead of print.ABSTRACTAdsorbates on metal surfaces are typically formed from the dissociative chemisorption of molecules occurring at gas-solid interfaces. These adsorbed species exhibit unique diffusion behaviors on metal surfaces, which are influenced by their translational energy. They play crucial roles in various fields, including heterogeneous catalysis and corrosion. This review examines recent theoretical advancements in understanding the diffusion dynamics of adsorbates on metal surfaces, with a specific emphasis on hydrogen and oxygen atom...
Source: Chemphyschem - March 21, 2024 Category: Chemistry Authors: Kaixuan Gu Sen Lin Source Type: research
On the Thermodynamic Equivalence of Grand Canonical, Infinite-Size, and Capacitor-Based Models in First-Principle Electrochemistry
Chemphyschem. 2024 Mar 21:e202300950. doi: 10.1002/cphc.202300950. Online ahead of print.ABSTRACTFirst principles-based computational and theoretical methods are constantly evolving trying to overcome the many obstacles towards a comprehensive understanding of electrochemical processes on an atomistic level. One of the major challenges has been the determination of reaction energetics under a constant potential. Here, a theoretical framework was proposed applying standard electronic structure methods and extrapolating to the infinite-cell size limit where reactions do not alter the potential. Today, electronically grand ca...
Source: Chemphyschem - March 21, 2024 Category: Chemistry Authors: Georg Kastlunger Sudarshan Vijay Xi Chen Shubham Sharma Andrew Peterson Source Type: research
Elastin-like Peptide as a Model for Disordered Proteins: Diffusion Behaviour in Self-Crowding Conditions
This study investigates the effect of crowding on the diffusion behaviour of an elastin-like peptide (ELP), by combined pulse field gradient (PFG) and static field gradient (SFG) NMR techniques. We interpret our findings in terms of highly dynamic chain assemblies with weak interactions, resulting in ELP diffusion that is primarily governed by the viscous flow of the solvent. The diffusion behaviour of the peptide appears to resemble that of globular proteins rather than flexible linear polymers over a wide concentration range.PMID:38511646 | DOI:10.1002/cphc.202400117 (Source: Chemphyschem)
Source: Chemphyschem - March 21, 2024 Category: Chemistry Authors: Susann Wei ßheit Bj örn Kuttich Michael Vogel Christina M Thiele Source Type: research
Structure-guided evolution of cyclohexanone monooxygenase toward bulky omeprazole sulfide: substrate migration and stereoselectivity inversion
Chemphyschem. 2024 Mar 21:e202400008. doi: 10.1002/cphc.202400008. Online ahead of print.ABSTRACTStructure-guided engineering of a CHMO from Amycolatopsis methanolica (AmCHMO) was performed for asymmetric sulfoxidation activity and stereoselectivity toward omeprazole sulfide. Initially, combinatorial active-site saturation test (CASTing) and iteratively saturation mutagenesis (ISM) were performed on 5 residues at the "bottleneck" of substrate tunnel, and MT3 was successfully obtained with a specific activity of 46.19 U/g and R-stereoselectivity of 99% toward OPS. Then, 4 key mutations affecting the stereoselectivity were i...
Source: Chemphyschem - March 21, 2024 Category: Chemistry Authors: Shiyu Wei Guochao Xu Jieyu Zhou Ye Ni Source Type: research
Infrared Laser Stark Spectroscopy of Methyl Fluoride in 4He Nanodroplets
The objective of performing Stark spectroscopy was to see if there is any evidence for a rotational linewidth dependence on the external field strength, due to a reduced difference in between methyl fluorides rotational energy gap and the roton-gap of superfluid helium. We did not find any evidence for such an effect, which we largely attribute to the rotational energy gap not increasing significantly enough by the external field. We point to another molecule (formaldehyde) whose energy levels are predicted to show a more promising response to application of an external field.PMID:38511250 | DOI:10.1002/cphc.202400224 (Source: Chemphyschem)
Source: Chemphyschem - March 21, 2024 Category: Chemistry Authors: Paul Raston Gary E Douberly Source Type: research
Advances in the Dynamics of Adsorbate Diffusion on Metal Surfaces: Focus on Hydrogen and Oxygen
Chemphyschem. 2024 Mar 21:e202400083. doi: 10.1002/cphc.202400083. Online ahead of print.ABSTRACTAdsorbates on metal surfaces are typically formed from the dissociative chemisorption of molecules occurring at gas-solid interfaces. These adsorbed species exhibit unique diffusion behaviors on metal surfaces, which are influenced by their translational energy. They play crucial roles in various fields, including heterogeneous catalysis and corrosion. This review examines recent theoretical advancements in understanding the diffusion dynamics of adsorbates on metal surfaces, with a specific emphasis on hydrogen and oxygen atom...
Source: Chemphyschem - March 21, 2024 Category: Chemistry Authors: Kaixuan Gu Sen Lin Source Type: research
On the Thermodynamic Equivalence of Grand Canonical, Infinite-Size, and Capacitor-Based Models in First-Principle Electrochemistry
Chemphyschem. 2024 Mar 21:e202300950. doi: 10.1002/cphc.202300950. Online ahead of print.ABSTRACTFirst principles-based computational and theoretical methods are constantly evolving trying to overcome the many obstacles towards a comprehensive understanding of electrochemical processes on an atomistic level. One of the major challenges has been the determination of reaction energetics under a constant potential. Here, a theoretical framework was proposed applying standard electronic structure methods and extrapolating to the infinite-cell size limit where reactions do not alter the potential. Today, electronically grand ca...
Source: Chemphyschem - March 21, 2024 Category: Chemistry Authors: Georg Kastlunger Sudarshan Vijay Xi Chen Shubham Sharma Andrew Peterson Source Type: research
