Quantum Chemical Determination of Molecular Dye Candidates for Non-Invasive Bioimaging.

Molecular dyes containing carbazole-based π bridges and/or julolidine-based donors should be promising molecules for intense SWIR emission with potential application to molecular bioimaging. This study stochastically analyzes the combinations of more than 250 organic dyes constructed within the D-π-D (or equivalently D-B-D) motif. These dyes are built from 22 donors (D) and 14 π bridges (B) and are computationally examined using density functional theory (DFT).

Infrared Spectroscopy of Isocyano-Polycyclic Aromatic Hydrocarbons: The NC Stretch.

Anharmonic computations reveal an intense, narrow (20 cm, 0.043 μm) absorption feature at approximately 2160 cm (4.63 μm) in the vibrational spectra of 14 prototypical singly isocyano-substituted polycyclic aromatic hydrocarbons (NC-PAHs) attributed to the NC stretching mode.

Computing Accurate & Reliable Rovibrational Spectral Data for Aluminum-Bearing Molecules.

The difficulty of quantum chemically computing vibrational, rotational, and rovibrational reference data via quartic force fields (QFFs) for molecules containing aluminum appears to be alleviated herein using a hybrid approach based upon CCSD(T)-F12b/cc-pCVTZ further corrected for conventional CCSD(T) scalar relativity within the harmonic terms and simple CCSD(T)-F12b/cc-pVTZ for the cubic and quartic terms: the F12-TcCR+TZ QFF. Aluminum containing molecules are theorized to participate in significant chemical processes in both the Earth's upper atmosphere as well as within circumstellar and interstellar media. However, experimental data for the identification of these molecules are limited, showcasing the potential for quantum chemistry to contribute significant amounts of spectral reference data.

Battle of the CH motions: aliphatic versus aromatic contributions to astronomical PAH emission and exploration of the aliphatic, aromatic, and ethynyl CH stretches.

Strong anharmonic coupling between vibrational states in polycyclic aromatic hydrocarbons (PAH) produces highly mixed vibrational transitions that challenge the current understanding of the nature of the astronomical mid-infrared PAH emission bands. Traditionally, PAH emission bands have been characterized as either aromatic or aliphatic, and this assignment is used to determine the fraction of aliphatic carbon in astronomical sources. In reality, each of the transitions previously utilized for such an attribution is highly mixed with contributions from both aliphatic and aromatic CH motions as well as non-CH motions such as CC stretches.

Computational Mechanistic Analysis of the Formation of the Magnesium Silicate Monomers MgSiO and MgSiO.

Silicate grains comprise a large fraction of cosmic dust, motivating a need to understand how they form. The current body of work on silicates generally reflects the abundance of silicate grains, yet models for their formation often do not consider silicate chemistry on the smallest scale, which can form species available for dust grain nucleation processes. In order to expand upon previous attempts to bridge this gap in silicate chemistry, novel gas-phase reaction pathways for the magnesium silicate monomers enstatite (MgSiO) and forsterite (MgSiO) from MgH, HO, and SiO are presently computed using highly accurate quantum chemical calculations.

Formation of Paraldehyde (CHO) in Interstellar Analog Ices of Acetaldehyde Exposed to Ionizing Radiation.

Acetaldehyde (CHCHO) plays a crucial role in the synthesis of prebiotic molecules such as amino acids, sugars, and sugar-related compounds, and in the progress of chain reaction polymerization in deep space. Here, we report the first formation of the cyclic acetaldehyde trimer - paraldehyde (CHO) - in low-temperature interstellar analog ices exposed to energetic irradiation as proxies of galactic cosmic rays (GCRs). Utilizing vacuum ultraviolet photoionization reflectron time-of-flight mass spectrometry and isotopic substitution experiments, paraldehyde was identified in the gas phase during the temperature-programmed desorption of the irradiated acetaldehyde ices based on the calculated adiabatic ionization energies and isomer-specific dissociative fragmentation patterns upon photoionization.

Vibrational and Rovibrational Spectroscopic Data for the Ground and First-Excited States of Phosgene (COCl), Formic Acid (HCOOH), and Chloroformic Acid (ClCOOH).

While "black box" quantum chemical computations for the determination of rovibronic spectral data are not quite at hand, the present work utilizes the titular molecules to showcase how excited-state quantum chemical methods can be conjoined to quartic force field (QFF) anharmonic rovibrational treatments to provide novel and useful predictions for such data. This work employs hybrid QFFs with explicitly correlated coupled cluster theory along with the equation-of-motion formalism to generate harmonic force constants and time-dependent density functional theory (TD-DFT) to produce anharmonic force constants for the generation of electronically excited-state rovibrational spectral data, in effect, rovibronic spectral data. Specific spectroscopic results from this work show that the fundamental C═O stretch in phosgene as well as in - and -formic acid drop from the region of around 1800 cm to close to 1100 cm or less in the first excited states of each molecule.

The fundamental vibrational frequencies and spectroscopic constants of the COH isomers: molecules known in simulated interstellar ice analogues.

While -glyoxal may not be easily observable in astronomical sources through either IR or radioastronomy due to its symmetry, its conformer along with the -HCOCO epoxide isomer should be ready targets for astrochemical detection. The present quantum chemical study shows that not only are both molecular isomers strongly polar, they also have notable IR features and low isomerisation energies of 4.1 kcal mol and 10.

Picking up Good Vibrations through Quartic Force Fields and Vibrational Perturbation Theory.

Quartic force fields (QFFs) define sparse potential energy surfaces (compared to semiglobal surfaces) that are the cheapest and easiest means of computing anharmonic vibrational frequencies, especially when utilized with second-order vibrational perturbation theory (VPT2). However, flat and shallow potential surfaces are exceedingly difficult for QFFs to treat through a combination of numerical noise in the often numerically computed derivatives and in competing energy factors in the composite energies often utilized to provide high-level spectroscopic predictions. While some of these issues can be alleviated with analytic derivatives, hybrid QFFs, and intelligent choices in coordinate systems, the best practice is for predicting good molecular vibrations via QFFs is to understand what they cannot do, and this manuscript documents such cases where QFFs may fail.

Rovibrational analysis of AlCO3, OAlO2, and HOAlO2 for possible atmospheric detection.

The lack of observational data for the AlO molecule in the mesosphere/lower thermosphere may be due to ablated aluminum reacting quickly to form other species. Previously proposed reaction pathways show that aluminum could be ablated in the atmosphere from meteoritic activity, but there currently exist very limited spectroscopic data on the intermediates in these reactions, limiting the possible detection of said molecules. As such, rovibrational spectroscopic data are computed herein using quartic force field methodology at four different levels of theory for the neutral intermediates AlCO3, OAlO2, and HOAlO2.

Assigning the CH stretch overtone spectrum of benzene and naphthalene with extension to anthracene and tetracene using 2- and 3-quanta anharmonic quantum chemical computations.

The CH stretch overtone region (5750-6300 cm-1) of benzene and naphthalene is assigned herein using anharmonic quantum chemical computations, and the trend of how this extends to larger polycyclic aromatic hydrocarbons (PAHs) is established. The assignment of all experimental bands to specific vibrational states is performed for the first time. Resonance polyads and the inclusion of 3-quanta vibrational states are both needed to compute accurate vibrational frequencies with the proper density-of-states to match the experimental band shape.

Theoretical Rotational and Vibrational Spectral Data for the Hypermagnesium Oxide Species MgO and MgO.

While magnesium is astronomically observed in small molecules, it largely serves as a contributor to silicate grains, though how these grains form is not well-understood. The smallest hypermagnesium oxide compounds (Mg O/Mg O ) may play a role in silicate formation, but little vibrational reference data exist. As such, anharmonic spectroscopic data are computed for Mg O, Mg O, and Mg O using quartic force fields (QFFs).

Bridging the gap: viable reaction pathways from tetrahedrane to benzyne.

The addition of sp-carbon-containing molecules to polycyclic sp tetrahedrane (-CH) results in the formation of both -benzyne (-CH) and benzene (-CH). Since both -CH and -CH have been detected in the interstellar medium (ISM), providing additional pathways for their possible astrochemical formation mechanisms can lead to the discovery of other molecules, such as -CH, benzvalyne, and vinylidene (:CCH). Addition of diatomic carbon (C), the ethynyl radical (CH), vinylidene, and acetylene (HCCH) to -CH is undertaken in individual pathways through high-level quantum chemical computations at the CCSD(T)-F12b/cc-pVTZ-F12 level of theory.

The infrared absorption spectrum of phenylacetylene and its deuterated isotopologue in the mid- to far-IR.

Anharmonicity strongly influences the absorption and emission spectra of polycyclic aromatic hydrocarbon (PAH) molecules. Here, IR-UV ion-dip spectroscopy experiments together with detailed anharmonic computations reveal the presence of fundamental, overtone, as well as 2- and 3-quanta combination band transitions in the far- and mid-infrared absorption spectra of phenylacetylene and its singly deuterated isotopologue. Strong absorption features in the 400-900 cm-1 range originate from CH(D) in-plane and out-of-plane wags and bends, as well as bending motions including the C≡C and CH bonds of the acetylene substituent and the aromatic ring.

Interstellar formation of glyceric acid [HOCHCH(OH)COOH]-The simplest sugar acid.

Glyceric acid [HOCHCH(OH)COOH]-the simplest sugar acid-represents a key molecule in biochemical processes vital for metabolism in living organisms such as glycolysis. Although critically linked to the origins of life and identified in carbonaceous meteorites with abundances comparable to amino acids, the underlying mechanisms of its formation have remained elusive. Here, we report the very first abiotic synthesis of racemic glyceric acid via the barrierless radical-radical reaction of the hydroxycarbonyl radical (HOĊO) with 1,2-dihydroxyethyl (HOĊHCHOH) radical in low-temperature carbon dioxide (CO) and ethylene glycol (HOCHCHOH) ices.

Performance of EOM-CCSD(T)(a)*-Based Quartic Force Fields in Computing Fundamental, Anharmonic Vibrational Frequencies of Molecular Electronically Excited States with Application to the ″ State of :CCH (Vinylidene).

Highly accurate anharmonic vibrational frequencies of electronically excited states are not as easily computed as their ground electronic state counterparts, but recently developed approximate triple excited state methods may be changing that. One emerging excited state method is equation of motion coupled cluster theory at the singles and doubles level with perturbative triples computed via the (a)* formalism, EOMEE-CCSD(T)(a)*. One of the most employed means for the ready computation of vibrational anharmonic frequencies for ground electronic states is second-order vibrational perturbation theory (VPT2), a theory based on quartic force fields (QFFs),fourth-order Taylor series expansions of the potential portion of the internuclear Watson Hamiltonian.

Quantum Chemistry and Astrochemistry: A Match Made in the Heavens.

Quantum chemistry can uniquely answer astrochemical questions that no other technique can provide. Computations can be parallelized, automated, and left to run continuously providing exceptional molecular throughput that cannot be done through experimentation. Additionally, the granularity of the individual computations that are required of potential energy surfaces, reaction mechanism pathways, or other quantum chemically derived observables produces a unique mosaic that make up the larger whole.

A Vision for the Future of Astrochemistry in the Interstellar Medium by 2050.

By 2050, many, but not nearly all, unattributed astronomical spectral features will be conclusively linked to molecular carriers (as opposed to nearly none today in the visible and IR); amino acids will have been observed remotely beyond our solar system; the largest observatories ever constructed on the surface of the Earth or launched beyond it will be operational; high-throughput computation either from brute force or machine learning will provide unprecedented amounts of reference spectral and chemical reaction data; and the chemical fingerprints of the universe delivered by those of us who call ourselves astrochemists will provide astrophysicists with unprecedented resolution for determining how the stars evolve, planets form, and molecules that lead to life originate. Astrochemistry is a relatively young field, but with the entire universe as its playground, the discipline promises to persist as long as telescopic observations are made that require reference data and complementary chemical modeling. While the recent commissionings of the and Atacama Large Millimeter Array are ushering in the second "golden age" of astrochemistry (with the first being the radio telescopic boom period of the 1970s), this current period of discovery should facilitate unprecedented advances within the next 25 years.

DFT + F12 QFFs for Cost-Effective Rovibrational Spectral Data Predictions of Ground and Excited Electronic States.

The quest for faster computation of anharmonic vibrational frequencies of both ground and excited electronic states has led to combining coupled cluster theory harmonic force constants with density functional theory cubic and quartic force constants for defining a quartic force field (QFF) utilized in conjunction with vibrational perturbation theory at second order (VPT2). This work shows that explicitly correlated coupled cluster theory at the singles, doubles, and perturbative triples levels [CCSD(T)-F12] provides accurate anharmonic vibrational frequencies and rotational constants when conjoined with any of B3LYP, CAM-B3LYP, BHandHLYP, PBE0, and ωB97XD for roughly one-quarter of the computational time of the CCSD(T)-F12 QFF alone for our test set. As the number of atoms in the molecule increases, however, the anharmonic terms become a greater portion of the QFF, and the cost comparison improves with HOCO and formic acid, requiring less than 15 and 10% of the time, respectively.

Spectroscopy and Photochemistry of OAlNO and Implications for New Metal Chemistry in the Atmosphere.

A new aluminum-bearing species, OAlNO, which has the potential to impact the chemistry of the Earth's upper atmosphere, is characterized via high-level, , spectroscopic methods. Meteor-ablated aluminum atoms are quickly oxidized to aluminum oxide (AlO) in the mesosphere and lower thermosphere (MLT), where a steady-state layer of AlO then builds up. Concurrent formation of nitric oxide (NO) in the same region of the atmosphere will lead to the bimolecular formation of the OAlNO molecule.

Spectroscopic Constants and Anharmonic Vibrational Frequencies of C(O)OC, c-CO and Their Silicon-Containing Analogues.

Comets are likely to contain various carbon oxide molecules potentially including C(O)OC and c-C2O2 on their surfaces and comae, as well as their silicon-substituted analogues possibly playing a role in the formation of interstellar dust grains. In this work, high-level quantum chemical data are provided to support such potential future astrophysical detection through the generation of predicted rovibrational data. Laboratory-based chemistry would also benefit from such aforementioned computational benchmarking considering these molecules' historic computational and experimental elusiveness.

F12+EOM Quartic Force Fields for Rovibrational Predictions of Electronically Excited States.

Quartic force fields (QFFs) constructed using a sum of ground-state CCSD(T)-F12b energies with EOM-CCSD excitation energies are proposed for computation of spectroscopic properties of electronically excited states. This is dubbed the F12+EOM approach and is shown to provide similar accuracy to previous methodologies at lower computational cost. Using explicitly correlated F12 approaches instead of canonical CCSD(T), as in the corresponding (T)+EOM approach, allows for 70-fold improvement in computational time.

pbqff: Push-Button Quartic Force Fields.

pbqff is an open-source program for fully automating the production of quartic force fields (QFFs) and their corresponding anharmonic spectroscopic data. Rather than being a monolithic piece of code, it consists of several key modules including a generic interface to quantum chemistry codes and, notably, queuing systems; a molecular point group symmetry library; an internal-to-Cartesian coordinate conversion module; a module for the ordinary least-squares fitting of potential energy surfaces; and an improved second-order rotational and vibrational perturbation theory package for asymmetric and symmetric tops that handles type-1 and -2 Fermi resonances, Fermi resonance polyads, and Coriolis resonances. All of these pieces are written in Rust, a modern, safe, and performant programming language that has much to offer for scientific programming.

Electronically excited states of closed-shell azabenzene and purine anion structures: Is 2 D enough for dipole-bound excited states?

Deprotonated azabenzene anions require dipole moments in their corresponding neutral radicals of more than 3.5 D in order to exhibit dipole-bound excited states (DBXSs). This is notably larger than the typical 2.

Complete, Theoretical Rovibronic Spectral Characterization of the Carbon Monoxide, Water, and Formaldehyde Cations.

New high-level ab initio quartic force field (QFF) methods are explored which provide spectroscopic data for the electronically excited states of the carbon monoxide, water, and formaldehyde cations, sentinel species for expanded, recent cometary spectral analysis. QFFs based on equation-of-motion ionization potential (EOM-IP) with a complete basis set extrapolation and core correlation corrections provide assignment for the fundamental vibrational frequencies of the A˜2B1 and B˜2A1 states of the formaldehyde cation; only three of these frequencies have experimental assignment available. Rotational constants corresponding to these vibrational excitations are also provided for the first time for all electronically excited states of both of these molecules.