Abstract. Uncertainties in the magnitude and seasonality of various gas emission modes, particularly among different lake types, limit our ability to estimate methane (CH4) and carbon dioxide (CO2) emissions from northern lakes. Here we assessed the relationship between CH4 and CO2 emission modes in 40 lakes along a latitudinal transect in Alaska to lakes' physicochemical properties and geographic characteristics, including permafrost soil type surrounding lakes. Emission modes included direct ebullition, diffusion, storage flux, and a newly identified ice-bubble storage (IBS) flux. We found that all lakes were net sources of atmospheric CH4 and CO2, but the climate warming impact of lake CH4 emissions was 2 times higher than that of CO2. Ebullition and diffusion were the dominant modes of CH4 and CO2 emissions, respectively. IBS, ~10% of total annual CH4 emissions, is the release to the atmosphere of seasonally ice-trapped bubbles when lake ice confining bubbles begins to melt in spring. IBS, which has not been explicitly accounted for in regional studies, increased the estimate of springtime emissions from our study lakes by 320%. Geographically, CH4 emissions from stratified, mixotrophic interior Alaska thermokarst (thaw) lakes formed in icy, organic-rich yedoma permafrost soils were 6-fold higher than from non-yedoma lakes throughout the rest of Alaska. The relationship between CO2 emissions and geographic parameters was weak, suggesting high variability among sources and sinks that regulate CO2 emissions (e.g., catchment waters, pH equilibrium). Total CH4 emission was correlated with concentrations of soluble reactive phosphorus and total nitrogen in lake water, Secchi depth, and lake area, with yedoma lakes having higher nutrient concentrations, shallower Secchi depth, and smaller lake areas. Our findings suggest that permafrost type plays important roles in determining CH4 emissions from lakes by both supplying organic matter to methanogenesis directly from thawing permafrost and by enhancing nutrient availability to primary production, which can also fuel decomposition and methanogenesis.

Abstract. Microbial methane (CH 4 ) ebullition (bubbling) from anoxic lake sediments comprises a globally significant flux to the atmosphere, but ebullition bubbles in temperate and polar lakes can be trapped by winter ice cover and later released during spring thaw. This "ice-bubble storage" (IBS) constitutes a novel mode of CH 4 emission. Before bubbles are encapsulated by downward-growing ice, some of their CH 4 dissolves into the lake water, where it may be subject to oxidation. We present field characterization and a model of the annual CH 4 cycle in Goldstream Lake, a thermokarst (thaw) lake in interior Alaska. We find that summertime ebullition dominates annual CH 4 emissions to the atmosphere. Eighty percent of CH 4 in bubbles trapped by ice dissolves into the lake water column in winter, and about half of that is oxidized. The ice growth rate and the magnitude of the CH 4 ebullition flux are important controlling factors of bubble dissolution. Seven percent of annual ebullition CH 4 is trapped as IBS and later emitted as ice melts. In a future warmer climate, there will likely be less seasonal ice cover, less IBS, less CH 4 dissolution from trapped bubbles, and greater CH 4 emissions from northern lakes.

Abstract. Uncertainties in the magnitude and seasonality of various gas emission modes, particularly among different lake types, limit our ability to estimate methane (CH4) and carbon dioxide (CO2) emissions from northern lakes. Here we assessed the relationship between CH4 and CO2 emission modes in 40 lakes along a latitudinal transect in Alaska to physicochemical limnology and geographic characteristics, including permafrost soil type surrounding lakes. Emission modes included Direct Ebullition, Diffusion, Storage flux, and a newly identified Ice-Bubble Storage (IBS) flux. We found that all lakes were net sources of atmospheric CH4 and CO2, but the climate warming impact of lake CH4 emissions was two times higher than that of CO2. Ebullition and Diffusion were the dominant modes of CH4 and CO2 emissions respectively. IBS, ~ 10% of total annual CH4 emissions, is the release to the atmosphere of seasonally ice-trapped bubbles when lake ice confining bubbles begins to melt in spring. IBS, which has not been explicitly accounted for in regional studies, increased the estimate of springtime emissions from our study lakes by 320%. Geographically, CH4 emissions from stratified, dystrophic interior Alaska thermokarst (thaw) lakes formed in icy, organic-rich yedoma permafrost soils were 6-fold higher than from non-yedoma lakes throughout the rest of Alaska. Total CH4 emission was correlated with concentrations of phosphate and total nitrogen in lake water, Secchi depth and lake area, with yedoma lakes having higher nutrient concentrations, shallower Secchi depth, and smaller lake areas. Our findings suggest that permafrost type plays important roles in determining CH4 emissions from lakes by both supplying organic matter to methanogenesis directly from thawing permafrost and by enhancing nutrient availability to primary production, which can also fuel decomposition and methanogenesis.

Semiclassical Transition State Theory (SCTST), a method for calculating rate constants of chemical reactions, offers gains in computational efficiency relative to more accurate quantum scattering methods. In full-dimensional (FD) SCTST, reaction probabilities are calculated from third and fourth potential derivatives along all vibrational degrees of freedom. However, the computational cost of FD SCTST scales unfavorably with system size, which prohibits its application to larger systems. In this study, the accuracy and efficiency of 1-D SCTST, in which only third and fourth derivatives along the reaction mode are used, are investigated in comparison to those of FD SCTST. Potential derivatives are obtained from numerical ab initio Hessian matrix calculations at the MP2/cc-pVTZ level of theory, and Richardson extrapolation is applied to improve the accuracy of these derivatives. Reaction barriers are calculated at the CCSD(T)/cc-pVTZ level. Results from FD SCTST agree with results from previous theoretical and experimental studies when Richardson extrapolation is applied. Results from our implementation of 1-D SCTST, which uses only 4 single-point MP2/cc-pVTZ energy calculations in addition to those for conventional TST, agree with FD results to within a factor of 5 at 250 K. This degree of agreement and the efficiency of the 1-D method suggest its potential as a means of approximating rate constants for systems too large for existing quantum scattering methods.

We introduce the "tensor-train split-operator Fourier transform" (TT-SOFT) method for simulations of multidimensional nonadiabatic quantum dynamics. TT-SOFT is essentially the grid-based SOFT method implemented in dynamically adaptive tensor-train representations. In the same spirit of all matrix product states, the tensor-train format enables the representation, propagation, and computation of observables of multidimensional wave functions in terms of the grid-based wavepacket tensor components, bypassing the need of actually computing the wave function in its full-rank tensor product grid space. We demonstrate the accuracy and efficiency of the TT-SOFT method as applied to propagation of 24-dimensional wave packets, describing the S/S interconversion dynamics of pyrazine after UV photoexcitation to the S state. Our results show that the TT-SOFT method is a powerful computational approach for simulations of quantum dynamics of polyatomic systems since it avoids the exponential scaling problem of full-rank grid-based representations.

Abstract. Microbial methane (CH4) ebullition (bubbling) from anoxic lake sediments comprises a globally significant flux to the atmosphere, but ebullition bubbles in temperate and polar lakes can be trapped by winter ice cover and later released during spring thaw. This "ice-bubble storage" (IBS) constitutes a novel mode of CH4 emission. Before bubbles are encapsulated by downward-growing ice, some of their CH4 dissolves into the lake water, where it may be subject to oxidation. We present field characterization and a model of the annual CH4 cycle in Goldstream Lake, a thermokarst (thaw) lake in interior Alaska. We find that summertime ebullition dominates annual CH4 emissions to the atmosphere. Eighty percent of CH4 in bubbles trapped by ice dissolves into the lake water column in winter, and about half of that is oxidized. The ice growth rate and the magnitude of the CH4 ebullition flux are important controlling factors of bubble dissolution. Seven percent of annual ebullition CH4 is trapped as IBS and later emitted as ice melts. In a future warmer climate, there will likely be less seasonal ice cover, less IBS, less CH4 dissolution from trapped bubbles, and greater CH4 emissions from northern lakes.

The inherent atomistic precision of synthetic chemistry enables bottom-up structural control over quantum bits, or qubits, for quantum technologies. Tuning paramagnetic molecular qubits that feature optical-spin initialization and readout is a crucial step toward designing bespoke qubits for applications in quantum sensing, networking, and computing. Here, we demonstrate that the electronic structure that enables optical-spin initialization and readout for S = 1, Cr(aryl) 4 , where aryl = 2,4dimethylphenyl (1), o-tolyl (2), and 2,3-dimethylphenyl (3), is readily translated into Cr(alkyl) 4 compounds, where alkyl = 2,2,2triphenylethyl (4), (trimethylsilyl)methyl ( 5), and cyclohexyl (6). The small ground state zero field splitting values (<5 GHz) for 1− 6 allowed for coherent spin manipulation at X-band microwave frequency, enabling temperature-, concentration-, and orientation-dependent investigations of the spin dynamics. Electronic absorption and emission spectroscopy confirmed the desired electronic structures for 4−6, which exhibit photoluminescence from 897 to 923 nm, while theoretical calculations elucidated the varied bonding interactions of the aryl and alkyl Cr 4+ compounds. The combined experimental and theoretical comparison of Cr(aryl) 4 and Cr(alkyl) 4 systems illustrates the impact of the ligand field on both the ground state spin structure and excited state manifold, laying the groundwork for the design of structurally precise optically addressable molecular qubits.

We investigate which terms in Reduced-Dimensionality Semiclassical Transition State Theory (RD SCTST) contribute most significantly in rate constant calculations of hydrogen extraction and exchange reactions of hydrocarbons. We also investigate the importance of deep tunneling corrections to the theory. In addition, we introduce a novel formulation of the theory in Jacobi coordinates. For the reactions of H atoms with methane, ethane, and cyclopropane, we find that a one-dimensional (1-D) version of the theory without deep tunneling corrections compares well with 2-D SCTST results and accurate quantum scattering results. For the "heavy-light-heavy" H atom exchange reaction between CH3 and CH4, deep tunneling corrections are needed to yield 1-D results that compare well with 2-D results. The finding that accurate rate constants can be obtained from derivatives of the potential along only one dimension further validates RD SCTST as a computationally efficient yet accurate rate constant theory.