Probing the Electronic Manifold of MgCl with Millimeter-Wave Spectroscopy and Theory: (3)Σ and (4)Σ States.

The millimeter/submillimeter spectrum of magnesium chloride (MgCl) has been observed in two new electronic excited states, (3)Σ and (4)Σ, using direct absorption methods. The molecule was synthesized in a mixture of Cl, argon, and magnesium vapor. For the (3)Σ state, multiple rotational transitions were measured in the = 0 level for all six isotopologues (MgCl, MgCl, MgCl, MgCl, MgCl, and MgCl), as well as up to = 13 for MgCl.

A DFT/MRCI Hamiltonian parameterized using only ab initio data. II. Core-excited states.

A newly parameterized combined density functional theory and multi-reference configuration interaction (DFT/MRCI) Hamiltonian, termed core-valence separation (CVS)-QE12, is defined for the computation of K-shell core-excitation and core-ionization energies. This CVS counterpart to the recently reported QE8 Hamiltonian [Costain et al., J.

Time Resolved Quantum Tomography in Molecular Spectroscopy by the Maximal Entropy Approach.

Attosecond science offers unprecedented precision in probing the initial moments of chemical reactions, revealing the dynamics of molecular electrons that shape reaction pathways. A fundamental question emerges: what role, if any, do quantum coherences between molecular electron states play in photochemical reactions? Answering this question necessitates quantum tomography─the determination of the electronic density matrix from experimental data, where the off-diagonal elements represent these coherences. The Maximal Entropy (MaxEnt) based Quantum State Tomography (QST) approach offers unique advantages in studying molecular dynamics, particularly with partial tomographic data.

Calculation of quasi-diabatic states within the DFT/MRCI(2) framework: The QD-DFT/MRCI(2) method.

We describe a procedure for the calculation of quasi-diabatic states within the recently introduced DFT/MRCI(2) framework [S. P. Neville and M.

A DFT/MRCI Hamiltonian parameterized using only ab initio data: I. valence excited states.

A new combined density functional theory and multi-reference configuration interaction (DFT/MRCI) Hamiltonian parameterized solely using the benchmark ab initio vertical excitation energies obtained from the QUEST databases is presented. This new formulation differs from all previous versions of the method in that the choice of the underlying exchange-correlation (XC) functional employed to construct the one-particle (orbital) basis is considered, and a new XC functional, QTP17, is chosen for its ability to generate a balanced description of core and valence vertical excitation energies. The ability of the new DFT/MRCI Hamiltonian, termed QE8, to furnish accurate excitation energies is confirmed using benchmark quantum chemistry computations, and a mean absolute error of 0.

Few-femtosecond electronic and structural rearrangements of driven by the Jahn-Teller effect.

The Jahn-Teller effect (JTE) is central to the understanding of the physical and chemical properties of a broad variety of molecules and materials. Whereas the manifestations of the JTE in stationary properties of matter are relatively well studied, the study of JTE-induced dynamics is still in its infancy, largely owing to its ultrafast and non-adiabatic nature. For example, the time scales reported for the distortion of from the initial geometry to a nominal relaxed structure range from 1.

Ultrafast Molecular Frame Quantum Tomography.

We develop and experimentally demonstrate a methodology for a full molecular frame quantum tomography (MFQT) of dynamical polyatomic systems. We exemplify this approach through the complete characterization of an electronically nonadiabatic wave packet in ammonia (NH_{3}). The method exploits both energy and time-domain spectroscopic data, and yields the lab frame density matrix (LFDM) for the system, the elements of which are populations and coherences.

Vulvar squamous cell carcinoma in women 80 years and older: Treatment, survival and impact of comorbidities.

Background: Despite being a disease of mainly older women, little is known about the clinical management of older women with vulvar squamous cell carcinoma (VSCC). We evaluated their daily clinical management compared with younger women, and established the prevalence of comorbidities and its impact on overall survival (OS).

Methods: All Dutch women diagnosed with VSCC from 2015 to 2020 (n = 2249) were selected from the Netherlands Cancer Registry.

The cancer burden in the oldest-old: Increasing numbers and disparities-A nationwide study in the Netherlands, 1990 to 2019.

Adults aged ≥80 years (the oldest-old) comprise the fastest growing age group in Western populations. Yet little is known about their cancer burden. In this nationwide study, we assessed their trends in incidence, treatment and survival over a 30-year period, and predicted their future cancer incidence.

Machine Learning Seams of Conical Intersection: A Characteristic Polynomial Approach.

The machine learning of potential energy surfaces (PESs) has undergone rapid progress in recent years. The vast majority of this work, however, has been focused on the learning of ground state PESs. To reliably extend machine learning protocols to excited state PESs, the occurrence of seams of conical intersections between adiabatic electronic states must be correctly accounted for.

Variation in the management of cT1 renal cancer by surgical hospital volume: A nationwide study.

Objectives: To analyse variation in clinical management of cT1 renal cell carcinoma (RCC) in the Netherlands related to surgical hospital volume (HV).

Materials And Methods: Patients diagnosed with cT1 RCC during 2014-2020 were identified in the Netherlands Cancer Registry. Patient and tumour characteristics were retrieved.

Effects and Working Mechanisms of a Multilevel Implementation Program for Applying Shared Decision-Making while Discussing Systemic Treatment in Breast Cancer.

Background: Enhancing the application of shared decision-making (SDM) is critical for integrating patient preferences in breast cancer treatment choices. We investigated the effect of an adapted multilevel SDM implementation program in breast cancer care. Methods: Breast cancer patients qualifying for (neo)adjuvant systemic treatment were included in a multicenter before−after study.

A perturbative approximation to DFT/MRCI: DFT/MRCI(2).

We introduce a perturbative approximation to the combined density functional theory and multireference configuration interaction (DFT/MRCI) approach. The method, termed DFT/MRCI(2), results from the application of quasi-degenerate perturbation theory (QDPT) and the Epstein-Nesbet partitioning to the DFT/MRCI Hamiltonian matrix. The application of QDPT obviates the need to diagonalize the large DFT/MRCI Hamiltonian; electronic energies are instead obtained as the eigenvalues of a small effective Hamiltonian, affording an orders of magnitude savings in the computational cost.

A laboratory frame density matrix for ultrafast quantum molecular dynamics.

In most cases, the ultrafast dynamics of resonantly excited molecules are considered and almost always computed in the molecular frame, while experiments are carried out in the laboratory frame. Here, we provide a formalism in terms of a lab frame density matrix, which connects quantum dynamics in the molecular frame to those in the laboratory frame, providing a transparent link between computation and measurement. The formalism reveals that in any such experiment, the molecular frame dynamics vary for molecules in different orientations and that certain coherences, which are potentially experimentally accessible, are rejected by the orientation-averaged reduced vibronic density matrix.

β1-Integrin-A Key Player in Controlling Pancreatic Beta-Cell Insulin Secretion via Interplay With SNARE Proteins.

Shortcomings in cell-based therapies for patients with diabetes have been revealed to be, in part, a result of an improper extracellular matrix (ECM) environment. In vivo, pancreatic islets are emersed in a diverse ECM that provides physical support and is crucial for healthy function. β1-Integrin receptors have been determined to be responsible for modulation of beneficial interactions with ECM proteins influencing beta-cell development, proliferation, maturation, and function.

N-acetyl-L-cysteine treatment reduces beta-cell oxidative stress and pancreatic stellate cell activity in a high fat diet-induced diabetic mouse model.

Obesity plays a major role in type II diabetes (T2DM) progression because it applies metabolic and oxidative stress resulting in dysfunctional beta-cells and activation of intra-islet pancreatic stellate cells (PaSCs) which cause islet fibrosis. Administration of antioxidant N-acetyl-L-cysteine (NAC) improves metabolic outcomes in diet-induced obese diabetic mice, and inhibits PaSCs activation. However, the effects of NAC on diabetic islets are unknown.

Breast cancer patients' most important quality of life themes for a radiotherapy decision aid.

Background And Aim: The BRASA patient decision aid (BRASA-PtDA) facilitates shared decision making for breast cancer patients (BCPs) facing a radiotherapy treatment decision. During evaluations, patients indicated the wish for quantitative information on side effects. Therefore, this study assessed BCPs opinion on which and how information on side effects should be incorporated in the BRASA-PtDA.

Peritoneal metastases in elderly patients with colorectal cancer.

Background: With the introduction of cytoreductive surgery with intraperitoneal chemotherapy and the development of new systemic anti-cancer agents, the treatment of colorectal cancer (CRC) patients with peritoneal metastases has changed. Real-world data on the treatment of elderly patients and their clinical outcomes is lacking.

Methods: All CRC patients diagnosed with synchronous peritoneal metastases (SPM) during 2008-2019 (n = 7,748) were identified from the Netherlands Cancer Registry.

Collagen IV-β1-Integrin Influences INS-1 Cell Insulin Secretion Enhanced SNARE Protein Expression.

β1-integrin is a key receptor that regulates cell-ECM interactions and is important in maintaining mature beta-cell functions, including insulin secretion. However, there is little reported about the relationship between ECM-β1-integrin interactions and exocytotic proteins involved in glucose-stimulated insulin secretion (GSIS). This study examined the effect of collagen IV-β1-integrin on exocytotic proteins (Munc18-1, Snap25, and Vamp2) involved in insulin secretion using rat insulinoma (INS-1) cell line.

Sex, Gender and Age Differences in Treatment Allocation and Survival of Patients With Metastatic Pancreatic Cancer: A Nationwide Study.

Background: Biological sex, gender and age have an impact on the incidence and outcome in patients with metastatic pancreatic cancer. The aim of this study is to investigate whether biological sex, gender and age are associated with treatment allocation and overall survival (OS) of patients with metastatic pancreatic cancer in a nationwide cohort.

Methods: Patients with synchronous metastatic pancreatic cancer diagnosed between 2015 and 2019 were selected from the Netherlands Cancer Registry (NCR).

Time-resolved photoelectron spectroscopy: the continuing evolution of a mature technique.

Time-resolved photoelectron spectroscopy (TRPES) has become one of the most widespread techniques for probing nonadiabatic dynamics in the excited electronic states of molecules. Furthermore, the complementary development of approaches for the simulation of TRPES signals has enabled the interpretation of these transient spectra in terms of underlying coupled electronic-nuclear dynamics. In this perspective, we discuss the current state-of-the-art approaches, including efforts to push femtosecond pulses into vacuum ultraviolet and soft X-ray regimes as well as the utilization of novel polarizations to use time-resolved optical activity as a probe of nonadiabatic dynamics.

A Comparison of Partial Atomic Charges for Electronically Excited States.

Partial atomic charges are a useful and intuitive concept for understanding molecular properties and chemical reaction mechanisms, showing how changes in molecular geometry can affect the flow of electronic charge within a molecule. However, the use of partial atomic charges remains relatively uncommon in the characterization of excited-state electronic structure. Here, we show how well-established partial atomic charge methods perform for interatomic, intermolecular, and interbond electron transfer in electronically excited states.

Electronic relaxation and dissociation dynamics in formaldehyde: pump wavelength dependence.

The effect of the incident UV pump wavelength on the subsequent excited state dynamics, electronic relaxation, and ultimate dissociation of formaldehyde is studied using first principles simulation and Coulomb explosion imaging (CEI) experiments. Transitions in a vibronic progression in the ← absorption band are systematically prepared using a tunable UV source which generates pulses centered at 304, 314, 329, and 337 nm. We find, both simulation and experimental results, that the rate of excited state decay and subsequent dissociation displays a prominent dependence on which vibronic transition in the absorption band is prepared by the pump.

Resolving competing conical intersection pathways: time-resolved X-ray absorption spectroscopy of -1,3-butadiene.

Time-resolved X-ray absorption spectroscopy is emerging as a uniquely powerful tool to probe coupled electronic-nuclear dynamics in photo-excited molecules. Theoretical studies to date have established that time-resolved X-ray absorption spectroscopy is an atom-specific probe of excited-state wave packet passage through a seam of conical intersections (CIs). However, in many molecular systems, there are competing dynamical pathways involving CIs of different electronic and nuclear character.