Potential energy surfaces for the HBr(+) + CO2 → Br + HOCO(+) reaction in the HBr(+) (2)Π3/2 and (2)Π1/2 spin-orbit states.

Quantum mechanical (QM) + molecular mechanics (MM) models are developed to represent potential energy surfaces (PESs) for the HBr(+) + CO2 → Br + HOCO(+) reaction with HBr(+) in the (2)Π3/2 and (2)Π1/2 spin-orbit states. The QM component is the spin-free PES and spin-orbit coupling for each state is represented by a MM-like analytic potential fit to spin-orbit electronic structure calculations. Coupled-cluster single double and perturbative triple excitation (CCSD(T)) calculations are performed to obtain "benchmark" reaction energies without spin-orbit coupling. With zero-point energies removed, the "experimental" reaction energy is 44 ± 5 meV for HBr(+)((2)Π3/2) + CO2 → Br((2)P3/2) + HOCO(+), while the CCSD(T) value with spin-orbit effects included is 87 meV. Electronic structure calculations were performed to determine properties of the BrHOCO(+) reaction intermediate and [HBr⋯OCO](+) van der Waals intermediate. The results of different electronic structure methods were compared with those obtained with CCSD(T), and UMP2/cc-pVTZ/PP was found to be a practical and accurate QM method to use in QM/MM direct dynamics simulations. The spin-orbit coupling calculations show that the spin-free QM PES gives a quite good representation of the shape of the PES originated by (2)Π3/2HBr(+). This is also the case for the reactant region of the PES for (2)Π1/2 HBr(+), but spin-orbit coupling effects are important for the exit-channel region of this PES. A MM model was developed to represent these effects, which were combined with the spin-free QM PES.

Dyadic positive and negative religious coping among older Singaporean couples and marital satisfaction.

Difficulties faced in life can affect marital relationships and such troubles may be dealt with in a multitude of ways, including coping religiously. The present study examined how religious coping, either in a positive or negative manner, may have an impact on marital satisfaction. Importantly, this association was studied dyadically in a sample of religiously diverse (Buddhists, 32.3%; Taoists, 17.6%; protestant Christians, 14.1%; and others who did not identify with a specific religion, 19.1%), married older Singaporean adults (N = 1928; 964 couples). Using actor-partner interdependence modeling, we found significant actor, partner, and combined actor-partner effects for positive and negative religious coping on marital satisfaction. Specifically, marital satisfaction was highest when both spouses reported high levels of positive religious coping and low levels of negative religious coping. Taken together, these findings suggest that it is the simultaneous act of either greater positive or lower negative religious coping by both spouses that is related to higher marital satisfaction. (PsycInfo Database Record (c) 2023 APA, all rights reserved).

Information trust and COVID-19 vaccine hesitancy amongst middle-aged and older adults in Singapore: A latent class analysis Approach.

RATIONALE: COVID-19 vaccine hesitancy presents significant challenges for public health. OBJECTIVE: Vaccine hesitancy among middle-aged and older adults has been a significant barrier in Singapore's battle against COVID-19. We hypothesize that the trust middle-aged and older adults place in various sources of information influences vaccine hesitancy, and that distinct typologies of trust can be identified to better inform targeted health communication efforts. METHOD: Data from a nationally representative panel survey of Singaporeans aged 56-75 (N = 6094) was utilized. Modules fielded in August and November 2020, and June 2021 were analyzed, assessing social networks, trust in sources of information, and vaccination status respectively. Predictors of vaccination status were first examined. Latent class analysis was then used to identify typologies of trust in various sources of information. RESULTS: Trust in formal sources of information (e.g government sources) is found to predict vaccination status among respondents. Contrary to expectations, trust in social media and informal sources (family and friends), and perceived social support did not predict vaccination status. Latent class analysis identified 4 typologies of respondents based on their patterns of trust in these sources. Significantly, it is found that a portion of respondents with low trust in formal sources of information have high trust in informal sources. The four distinct typologies of trust in sources of information are also found to predict vaccination status. CONCLUSIONS: Because trust in formal sources of information influences vaccination status, authorities should build trust in such sources to encourage vaccination against COVID-19. However, health communication strategies with middle-aged and older adults who have low levels of trust in the formal sources may be more effective if authorities leveraged alternative channels such as informal sources, including the social networks of such individuals. Overall, the findings suggest the need for targeted communication strategies to encourage vaccination.