Vibrational treatment of hydroxylamine in valence coordinates.

A valence coordinate H2NOH ground state potential energy surface accurate for all levels up to 6000 cm-1 relative to trans zero point energy has been generated at the coupled-cluster single double triple-F12/aug-cc-pVTZ level encompassing the trans and cis as well as the N-H2 permutational conformers. All cis and trans fundamentals and a complete set of eigenfunctions up to about 3100 cm-1 have been calculated and assigned using the improved relaxation method of the Heidelberg multi-configuration time-dependent Hartree package and an exact expression for the kinetic energy in valence coordinates generated by the TANA program. The average and maximal error to all observed transitions is about 6.3 and 14.6 cm-1, respectively. Local cis eigenfunctions exist with up to two quanta in the isomerization mode ν9. Although no significant inversion splittings have been found up to the considered 3100 cm-1, they are expected within the fundamental energy range in view of the calculated 4261 cm-1 H2 permutation/inversion barrier height. The cis-NH2 symmetric stretch fundamental shows a Fermi resonance with a splitting of about 10 cm-1.

Train at home, but not alone: a randomised controlled multicentre trial assessing the effects of live-streamed tele-exercise during COVID-19-related lockdowns.

OBJECTIVE: Public life restrictions associated with the COVID-19 pandemic caused reductions in physical activity (PA) and decreases in mental and somatic health. Considering the interplay between these factors, we investigated the effects of digital home exercise (DHE) during government-enforced lockdowns. METHODS: A multicentre randomised controlled trial was performed allocating healthy individuals from nine countries (N=763; 523 female) to a DHE or an inactive control group. During the 4-week main intervention, DHE members engaged in live-streamed multicomponent home exercise. Subsequently, both groups had access to prerecorded workouts for an additional 4 weeks. Outcomes, assessed weekly, included PA level (Nordic Physical Activity Questionnaire-Short), anxiety (Generalized Anxiety Disorder Scale-7), mental well-being (WHO-5 Questionnaire), sleep quality (Medical Outcome Study Sleep Scale), pain/disability (Chronic Pain Grade Scale) and exercise motivation (Self-Concordance Scale). Mixed models were used for analysis. RESULTS: Live-streamed DHE consistently increased moderate PA (eg, week 1: 1.65 times more minutes per week, 95% CI 1.40 to 1.94) and vigorous PA (eg, week 1: 1.31 times more minutes per week, 95% CI 1.08 to 1.61), although the effects decreased over time. In addition, exercise motivation, sleep quality and anxiety were slightly improved for DHE in the 4-week live streaming period. The same applied to mental well-being (mean difference at week 4: +0.99, 95% CI 0.13 to 1.86), but an inverted trend was observed after live streaming was substituted by prerecorded exercise. CONCLUSIONS: Live-streamed DHE represents an efficacious method to enhance PA and selected markers of health during pandemic-related public life restrictions. However, research on implementation is warranted to reduce dropout rates. TRIAL REGISTRATION NUMBER: DRKS00021273.

Vibrational treatment of the formic acid double minimum case in valence coordinates.

One single full dimensional valence coordinate HCOOH ground state potential energy surface accurate for both cis and trans conformers for all levels up to 6000 cm-1 relative to trans zero point energy has been generated at CCSD(T)-F12a/aug-cc-pVTZ level. The fundamentals and a set of eigenfunctions complete up to about 3120 and 2660 cm-1 for trans- and cis-HCOOH, respectively, have been calculated and assigned using the improved relaxation method of the Heidelberg multi-configuration time-dependent Hartree package and an exact expression for the kinetic energy in valence coordinates generated by the TANA program. The calculated trans fundamental transition frequencies agree with experiment to within 5 cm-1. A few reassignments are suggested. Our results discard any cis trans delocalization effects for vibrational eigenfunctions up to 3640 cm-1 relative to trans zero point energy.

Fast Growing Plantations for Wood Production - Integration of Ecological Effects and Economic Perspectives.

Biomass crops are perceived as a feasible means to substitute sizeable amounts of fossil fuel in the future. A prospect of CO2 reduction (resp. CO2 neutrality) is credited to biomass fuels, and thus a potential contribution to mitigate climate change. Short rotation coppices (SRCs) with fast growing poplar and willow trees are an option for producing high yields of woody biomass, which is suitable for both energetic and material use. One negative effect that comes along with the establishment of SRC may be a decrease in groundwater recharge, because high rates of transpiration and interception are anticipated. Therefore, it is important to measure, analyze, and model the effects of SRC-planting on landscape water budgets. To analyze the effects on the water budget, a poplar SRC plot was studied by measuring hydrological parameters to be used in the hydrological model WaSim. Results reveal very low or even missing ground water recharge for SRC compared to agricultural land use or grassland, especially succeeding dry years. However, this strong effect on plot level is moderated on the larger spatial scale of catchment level, for which the modeling was also performed. In addition to water, nutrient fluxes and budgets were studied. Nitrogen is still a crucial issue in today's agriculture. Intensive fertilization or increased applications of manure from concentrated livestock breeding are often leading to high loads of nitrate leaching, or enhanced N2O emissions to the atmosphere on arable crop fields. SRC or agroforestry systems on former crop land may offer an option to decrease such N losses, while simultaneously producing woody biomass. This is mainly due to the generally smaller N requirements of woody vegetation, which usually entail no need for any fertilization. The trees supply deep and permanent rooting systems, which can be regarded as a "safety net" to prevent nutrient leaching. Thus, SRC altogether can help to diminish N eutrophication. It is important to offer viable and attractive economic perspectives to farmers and other land managers besides of the potential ecological benefits of SRCs. For this reason, an integrated tool for scenario analysis was developed within the BEST project ("BEAST - Bio-Energy Allocation and Scenario Tool"). It combines ecological assessments with calculations of economic revenue as a basis for a participative regional dialog on sustainable land use and climate protection goals. Results show a substantial capacity for providing renewable energy from economically competitive arable SRC sites while generating ecological synergies.

Gas-phase infrared spectra of three compounds of astrochemical interest: vinyl, allenyl, and propargyl isocyanides.

Isocyanides, isomers of the cyanides detected in the interstellar medium, are also possible components of this medium. The infrared spectra (5000-500 cm(-1) ) of gaseous vinyl isocyanide, allenyl isocyanide, and propargyl isocyanide have been recorded at 0.1 cm(-1) resolution. When prepared on a gram scale to produce a partial pressure of 10 mbar after evaporation in the cell, these three isocyanides, which have previously been reported to be kinetically unstable, do not display any sign of decomposition when recording the spectra. Geometry optimizations and harmonic and anharmonic vibrational frequencies were calculated using the LCCSD(T) method with the cc-pVTZ basis set. Anharmonic frequencies of fundamental, overtone, and combination transitions were calculated using a variational approach implemented in the P Anhar.v2.0 code, to assign the experimental data for each compound. These results improve our knowledge of these under-investigated compounds and pave the way for other physicochemical studies on functionalized isocyanides.

Theoretical investigation of intramolecular vibrational energy redistribution in HFCO and DFCO induced by an external field.

The present paper is devoted to a full quantum mechanical study of the intramolecular vibrational energy redistribution in HFCO and DFCO. In contrast to our previous studies [Pasin et al., J. Chem. Phys. 124, 194304 (2006) and 126, 024302 (2007)], the dynamics is now performed in the presence of an external time-dependent field. This more closely reflects the experimental conditions. A six-dimensional dipole surface is computed. The multiconfiguration time-dependent Hartree method is exploited to propagate the corresponding six-dimensional wave packets. Special emphasis is placed on the excitation of the out-of-plane bending vibration and on the dissociation of the molecule. In the case of DFCO, we predict that it is possible to excite the out-of-plane bending mode of vibration and to drive the dissociation to DF+CO with only one laser pulse with a fixed frequency and without excitation of an electronic state.

Time-dependent wave packet study on trans-cis isomerization of HONO driven by an external field.

The present paper is devoted to a full quantum mechanical study of the cis-->trans isomerization of HONO. In contrast to our previous study [Richter et al., J. Chem. Phys. 120, 6072 (2004)], the dynamics is now performed in the presence of an external time-dependent field in order to be closer to experimental conditions. A six-dimensional dipole surface is computed. Using a previously developed potential energy surface [Richter et al., J. Chem. Phys. 120, 1306 (2004)], all eigenstates up to 4000 cm(-1) are calculated. We simulate the dynamics during and after excitation by an electromagnetic pulse whose parameters are chosen to efficiently trigger the isomerization. Our investigations show that there is a selective isomerization pathway.

Time-dependent wave packet study on trans-cis isomerization of HONO.

Using a full six-dimensional ab initio potential energy surface and nuclear motion Hamiltonian, time-dependent computations were performed for the cis-trans isomerization of HONO. The multiconfiguration time-dependent Hartree method was used to propagate the six-dimensional wave packets. The initial excitations were chosen to be excitations of the local stretch modes and the HON local bend mode. The energy redistribution within 2 to 5 ps in the energy region of the OH stretching modes in both isomers was analyzed. The Fourier transformed frequency domain spectra were attributed to the eigenstates calculated previously by the time-independent variational approach. The results are also compared with classical trajectory computations of Thomson et al. on empirical surfaces. In agreement with matrix experiments, the cis-->trans isomerization was found to be much faster than the opposite interconversion. The intramolecular dynamics were found to be very complex involving numerous weakly excited delocalized eigenstates and anharmonic resonances. Particularly in the cis-isomer, the excitation of the HON bending local mode leads to fast energy redistribution in cis-trans delocalized modes. Neither the excitation of the OH stretching local mode in the cis nor in the trans form produces a fast isomerization, in agreement with the strongly localized characters of the corresponding eigenstates calculated variationally by Richter et al. and the gas phase spectra of HONO.

A study of the mode-selective trans--cis isomerization in HONO using ab initio methodology.

Ab initio calculations on the six-dimensional cis--trans double minimum potential energy surface of the electronic ground state of the HONO molecule were performed using a coupled cluster approach. An analytic fit to the data points was established. The interconversion barrier was calculated to be 4105 cm(-1). The nuclear motion problem was solved variationally using a full six-dimensional Hamiltonian in internal coordinates. The eigenstates up to about 3650 cm(-1) were tentatively assigned by harmonic quantum numbers. The assignment was based on the mean values of the internal coordinates of the six-dimensional eigenfunctions and on a comparison of the eigenenergies with those calculated by second-order perturbation theory from a full quartic force field in dimensionless normal coordinates. In cold matrices the trans- and the cis-OH nu(1) stretching modes and the first trans- and cis-NO 2nu(2) stretching overtones lead to isomerization. In the isolated molecule these modes (J=0) were found to be entirely localized. However, several overtones of the nu(4) ONO bending and nu(5) N-O stretching, which are close in energy to the OH stretch and combined with the torsional mode, were found to be strongly cis-trans delocalized.