Accurate approach in simulating the electronic absorption cross section of small to medium molecules

Sulfuric acid (H2SO4) is the dominant form of atmospheric sulfur in the stratosphere and plays an important role in terms of aerosol formation.The Absorption spectrum of sulfuric acid is simulated. Also in this work three photodissociation mechanisms of H2SO4 are calculated and found significant

Explicit correlation and basis set superposition error: The structure and energy of carbon dioxide dimer

We have investigated the slipped parallel and t-shaped structures of carbon dioxide dimer [(CO₂)₂] using both conventional and explicitly correlated coupled cluster methods, inclusive and exclusive of counterpoise (CP) correction. We have determined the geometry of both structures with conventional coupled cluster singles doubles and perturbative triples theory [CCSD(T)] and explicitly correlated cluster singles doubles and perturbative triples theory [CCSD(T)-F12b] at the complete basis set (CBS) limits using custom optimization routines. Consistent with previous investigations, we find that the slipped parallel structure corresponds to the global minimum and is 1.09 kJ mol⁻¹ lower in energy. For a given cardinal number, the optimized geometries and interaction energies of (CO₂)₂ obtained with the explicitly correlated CCSD(T)-F12b method are closer to the CBS limit than the corresponding conventional CCSD(T) results. Furthermore, the magnitude of basis set superposition error (BSSE) in the CCSD(T)-F12b optimized geometries and interaction energies is appreciably smaller than the magnitude of BSSE in the conventional CCSD(T) results. We decompose the CCSD(T) and CCSD(T)-F12b interaction energies into the constituent HF or HF CABS, CCSD or CCSD-F12b, and (T) contributions. We find that the complementary auxiliary basis set (CABS) singles correction and the F12b approximation significantly reduce the magnitude of BSSE at the HF and CCSD levels of theory, respectively. For a given cardinal number, we find that non-CP corrected, unscaled triples CCSD(T)-F12b/VXZ-F12 interaction energies are in overall best agreement with the CBS limit

XH-stretching overtone transitions calculated using explicitly correlated coupled cluster methods

We have calculated XH-stretching (where X=O, C, F, Cl) fundamental and overtone transitions for three diatomics and a few small molecules using a local mode model. The potential energy curves and dipole moment functions are calculated using the recently developed explicitly correlated coupled cluster with single doubles and perturbative triples theory [CCSD_T_-F12] with the associated VXZ-F12 (where X=D, T, Q) basis sets. We find that the basis set convergence of calculated frequencies and oscillator strengths obtained with the explicitly correlated method is much more rapid than with conventional CCSD(T) and the Dunning type correlation consistent basis sets. Furthermore, CCSD(T)-F12 frequencies and oscillator strengths obtained with the VTZ-F12 and VQZ-F12 basis sets are found to be in excellent agreement with the CCSD(T) complete basis set limit. We find that comparison of CCSD(T)-F12 frequencies with experiment is less good. The inclusion of explicit correlation exposes the inherent error of the CCSD(T) method to overestimate vibrational frequencies, which is normally compensated by basis set incompleteness error. As a consequence, we suggest that conventional CCSD(T) in combination with the aug-cc-pVTZ or aug-cc-pVQZ basis sets is likely to yield calculated XH-stretching frequencies in closest agreement with experiment

Switching to the rubber hand

Inducing the rubber hand illusion (RHI) requires that participants look at an imitation hand while it is stroked in synchrony with their occluded biological hand. Previous explanations of the RHI have emphasized multisensory integration, and excluded higher cognitive functions. We investigated the relationship between the RHI and higher cognitive functions by experimentally testing task switch (as measured by switch cost) and mind wandering (as measured by SART score); we also included a questionnaire for attentional control that comprises two subscales, attention-shift and attention-focus. To assess experience of RHI, the Botvinick and Cohen (1998) questionnaire was used and illusion onset time was recorded. Our results indicate that rapidity of onset reliably indicates illusion strength. Regression analysis revealed that participants evincing less switch cost and higher attention-shift scores had faster RHI onset times, and that those with higher attention-shift scores experienced the RHI more vividly. These results suggest that the multi-sensory hypothesis is not sufficient to explain the illusion: higher cognitive functions should be taken into account when explaining variation in the experience of ownership for the rubber hand

Explicitly correlated intermolecular distances and interaction energies of hydrogen bonded complexes

We have optimized the lowest energy structures and calculated interaction energies for the H2O–H2O, H2O–H2S, H2O–NH3, and H2O–PH3 dimers with the recently developed explicitly correlated CCSD(T)-F12 methods and the associated VXZ-F12 (where X=D,T,Q) basis sets. For a given cardinal number, we find that the results obtained with the CCSD(T)-F12 methods are much closer to the CCSD(T) complete basis set limit than the conventional CCSD(T) results. In general we find that CCSD(T)-F12 results obtained with the VTZ-F12 basis set are better than the conventional CCSD(T) results obtained with an aug-cc-pV5Z basis set. We also investigate two ways to reduce the effects of basis set superposition error with conventional CCSD(T), namely, the popular counterpoise correction and limiting diffuse basis functions to the heavy atoms only. We find that for a given cardinal number, these selectively augmented correlation consistent basis sets yield results that are closer to the complete basis set limit than the corresponding fully augmented basis sets. Furthermore, we find that the difference between standard and counterpoise corrected interaction energies and intermolecular distances is reduced with the selectively augmented basis sets

Explicit correlation and intermolecular interactions: Investigating carbon dioxide complexes with the CCSD(T)-F12 method

We have optimized the lowest energy structures and calculated interaction energies for the CO₂–Ar, CO₂–N₂, CO₂–CO, CO₂–H₂O, and CO₂–NH₃ dimers with the recently developed explicitly correlated coupled cluster singles doubles and perturbative triples [CCSD(T)]-F12 methods and the associated VXZ-F12 (where X = D,T,Q) basis sets. For a given cardinal number, we find that results obtained with the CCSD(T)-F12 methods are much closer to the CCSD(T) complete basis set limit than the conventional CCSD(T) results. The relatively modest increase in the computational cost between explicit and conventional CCSD(T) is more than compensated for by the impressive accuracy of the CCSD(T)-F12 method. We recommend use of the CCSD(T)-F12 methods in combination with the VXZ-F12 basis sets for the accurate determination of equilibrium geometries and interaction energies of weakly bound electron donor acceptor complexes

Quantifying cooperative intermolecular interactions for improved carbon dioxide capture materials

We have optimized the geometry and calculated interaction energies for over 100 different complexes of CO₂ with various combinations of electron accepting (Lewis acid) and electron donating (Lewis base) molecules. We have used the recently developed explicitly correlated coupled cluster singles doubles and perturbative triples [CCSD(T)-F12] methods and the associated VXZ-F12 (where X = D,T,Q) basis sets. We observe only modest changes in the geometric parameters of CO₂ upon complexation, which suggests that the geometry of CO₂ adsorbed in a nanoporous material should be similar to that of CO₂ in gas phase. When CO₂ forms a complex with two Lewis acids via the two electron rich terminal oxygen atoms, the interaction energy is less than twice what would be expected for the same complex involving a single Lewis acid. We consider a series of complexes that exhibit simultaneous CO₂-Lewis acid and CO₂-Lewis base intermolecular interactions, with total interaction energies spanning 14.1–105.9 kJ mol⁻¹. For these cooperative complexes, we find that the total interaction energy is greater than the sum of the interaction energies of the constituent complexes. Furthermore, the intermolecular distances of the cooperative complexes are contracted as compared to the constituent complexes. We suggest that metal-organic-framework or similar nanoporous materials could be designed with adsorption sites specifically tailored for CO₂ to allow cooperative intermolecular interactions, facilitating enhanced CO₂ adsorption

Networks and knowledge: a potted history

This research project explores the relationship between knowledge, and the organisation of production in the ‘Potteries’ district in North Staffordshire from 1750 to 1850