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1. The Parallel Reversible Pebbling Game: Analyzing the Post-quantum Security of iMHFs

   Blocki, Jeremiah; Holman, Blake; Lee, Seunghoon (December 2022, Theory of Cryptography Conference (TCC 2022))

   Kiltz, E. (Ed.)

   The classical (parallel) black pebbling game is a useful abstraction which allows us to analyze the resources (space, space-time, cumulative space) necessary to evaluate a function f with a static data-dependency graph G. Of particular interest in the field of cryptography are data-independent memory-hard functions fG,H which are defined by a directed acyclic graph (DAG) G and a cryptographic hash function H. The pebbling complexity of the graph G characterizes the amortized cost of evaluating fG,H multiple times as well as the total cost to run a brute-force preimage attack over a fixed domain X, i.e., given y∈{0,1}∗ find x∈X such that fG,H(x)=y. While a classical attacker will need to evaluate the function fG,H at least m=|X| times a quantum attacker running Grover’s algorithm only requires O(m−−√) blackbox calls to a quantum circuit CG,H evaluating the function fG,H. Thus, to analyze the cost of a quantum attack it is crucial to understand the space-time cost (equivalently width times depth) of the quantum circuit CG,H. We first observe that a legal black pebbling strategy for the graph G does not necessarily imply the existence of a quantum circuit with comparable complexity—in contrast to the classical setting where any efficient pebbling strategy for G corresponds to an algorithm with comparable complexity for evaluating fG,H. Motivated by this observation we introduce a new parallel reversible pebbling game which captures additional restrictions imposed by the No-Deletion Theorem in Quantum Computing. We apply our new reversible pebbling game to analyze the reversible space-time complexity of several important graphs: Line Graphs, Argon2i-A, Argon2i-B, and DRSample. Specifically, (1) we show that a line graph of size N has reversible space-time complexity at most O(N^{1+2/√logN}). (2) We show that any (e, d)-reducible DAG has reversible space-time complexity at most O(Ne+dN2^d). In particular, this implies that the reversible space-time complexity of Argon2i-A and Argon2i-B are at most O(N^2 loglogN/√logN) and O(N^2/(log N)^{1/3}), respectively. (3) We show that the reversible space-time complexity of DRSample is at most O((N^2loglog N)/log N). We also study the cumulative pebbling cost of reversible pebblings extending a (non-reversible) pebbling attack of Alwen and Blocki on depth-reducible graphs. 

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2. Dual functions of CO ₂ molecular activation and 4f levels as electron transport bridges in erbium single atom composite photocatalysts therefore enhancing visible-light photoactivities

   https://doi.org/10.1039/D1TA02926F  

   Chen, Qiuyu; Gao, Guoyang; Zhang, Yanzhou; li, Yini; Zhu, Hongyang; Zhu, Peifen; Qu, Yang; Wang, Guofeng; Qin, Weiping (July 2021, Journal of Materials Chemistry A)

   Only when the interfacial charge separation is enhanced and the CO 2 activation is improved, can the heterojunction nanocomposite photocatalyst be brought into full play for the CO 2 reduction reaction (CO 2 RR). Here, Er 3+ single atom composite photocatalysts were successfully constructed based on both the special role of Er 3+ single atoms and the special advantages of the SrTiO 3 :Er 3+ /g-C 3 N 4 heterojunction in the field of photocatalysis for the first time. As we expected, the SrTiO 3 :Er 3+ /g-C 3 N 4 (22.35 and 16.90 μmol g −1 h −1 for CO and CH 4 ) exhibits about 5 times enhancement in visible-light photocatalytic activity compared to pure g-C 3 N 4 (4.60 and 3.40 μmol g −1 h −1 for CO and CH 4 ). In particular, the photocatalytic performance of SrTiO 3 :Er 3+ /g-C 3 N 4 is more than three times higher than that of SrTiO 3 /g-C 3 N 4 . From Er 3+ fluorescence quenching measurements, photoelectrochemical studies, transient PL studies and DFT calculations, it is verified that a small fraction of surface doping of Er 3+ formed Er single-atoms on SrTiO 3 building an energy transfer bridge between the interface of SrTiO 3 and g-C 3 N 4 , resulting in enhanced interfacial charge separation. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC HAADF-STEM) and adsorption energy calculations demonstrated that the exposed Er single-atoms outside the interface on SrTiO 3 preferentially activate the adsorbed CO 2 , leading to the high photoactivity for the CO 2 RR. A novel enhanced photocatalytic mechanism was proposed, in which Er single-atoms play dual roles of an energy transfer bridge and activating CO 2 to promote charge separation. This provides new insights and feasible routes to develop highly efficient photocatalytic materials by engineering rare-earth single-atom doping. 

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3. Spectroscopic and Crystallographic Characterization of the R ₃ N ⁺ −C−H⋅⋅⋅X Interaction

   https://doi.org/10.1002/chem.202103922  

   Capilato, Joseph_N; Harry, Stefan_A; Siegler, Maxime_A; Lectka, Thomas (January 2022, Chemistry – A European Journal)

   Abstract As appreciation for nonclassical hydrogen bonds has progressively increased, so have efforts to characterize these interesting interactions. Whereas several kinds of C−H hydrogen bonds have been well‐studied, much less is known about the R₃N⁺−C−H⋅⋅⋅X variety. Herein, we present crystallographic and spectroscopic evidence for the existence of these interactions, with special relevance to Selectfluor chemistry. Of particular note is the propensity for Lewis bases to engage in nonclassical hydrogen bonding over halogen bonding with the electrophilic F atom of Selectfluor. Further, the first examples of¹H NMR experiments detailing R₃N⁺−C−H⋅⋅⋅X (X=O, N) hydrogen bonds are described. 

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4. Emergent Sasaki-Einstein geometry and AdS/CFT

   https://doi.org/10.1038/s41467-021-27951-9  

   Berman, Robert J.; Collins, Tristan C.; Persson, Daniel (December 2022, Nature Communications)

   Abstract A central problem in any quantum theory of gravity is to explain the emergence of the classical spacetime geometry in some limit of a more fundamental, microscopic description of nature. The gauge/gravity-correspondence provides a framework in which this problem can, in principle, be addressed. This is a holographic correspondence which relates a supergravity theory in five-dimensional Anti-deSitter space to a strongly coupled superconformal gauge theory on its 4-dimensional flat Minkowski boundary. In particular, the classical geometry should therefore emerge from some quantum state of the dual gauge theory. Here we confirm this by showing how the classical metric emerges from a canonical state in the dual gauge theory. In particular, we obtain approximations to the Sasaki-Einstein metric underlying the supergravity geometry, in terms of an explicit integral formula involving the canonical quantum state in question. In the special case of toric quiver gauge theories we show that our results can be computationally simplified through a process of tropicalization. 

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5. Ultraviolet Photodissociation Dynamics of the 1-Methylallyl Radical

   https://doi.org/10.1021/acs.jpca.4c02535  

   Lucas, Michael; Qin, Yuan; Yang, Lei; Sun, Ge; Zhang, Jingsong (July 2024, The Journal of Physical Chemistry A)

   The ultraviolet (UV) photodissociation dynamics of the 1-methylallyl (1-MA) radical were studied using the high-n Rydberg atom time-of-flight (HRTOF) technique in the wavelength region of 226–244 nm. The 1-MA radicals were produced by 193 nm photodissociation of the 3-chloro-1-butene and 1-chloro-2-butene precursor. The 1 + 1 REMPI spectrum of 1-MA agrees with the previous UV absorption spectrum in this wavelength region. Quantum chemistry calculations show that the UV absorption is mainly attributed to the 3pz Rydberg state (perpendicular to the allyl plane). The H atom photofragment yield (PFY) spectrum of 1-MA from 3-chloro-1-butene displays a broad peak around 230 nm, while that from 1-chloro-2-butene peaks at ∼236 nm. The translational energy distributions of the H atom loss product channel, P (ET)’s, show a bimodal distribution indicating two dissociation pathways in 1-MA. The major pathway is isotropic in product angular distribution with β ∼ 0 and has a low fraction of average translational energy in the total excess energy, ⟨fT⟩, in the range of 0.13–0.17; this pathway corresponds to unimolecular dissociation of 1-MA after internal conversion to form 1,3-butadiene + H. The minor pathway is anisotropic with β ∼ −0.23 and has a large ⟨fT⟩ of ∼0.62–0.72. This fast pathway suggests a direct dissociation of the methyl H atom on a repulsive excited state surface or the repulsive part of the ground state surface to form 1,3-butadiene + H. The fast/slow pathway branching ratio is in the range of 0.03–0.08. 

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