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Lou Massa

Publications and source records attributed to Lou Massa.

13 recordsLinked to original sources
arXiv2026

Benchmarking Astrochemistry Paradigms: Relative Absence of C6H5CN+ in the Diffuse ISM

The detectability of C6H5CN+ (benzonitrile cation) in the diffuse ISM is re-evaluated. A holistic evidentiary framework suggests C6H5CN+ is relatively absent in the diffuse ISM owing to the following concurrently: a marginal intramolecular vibrational energy redistribution (IVR) favoring fragmentation, recurrent fluorescence being an improbable mechanism in this case to prevent dissociation, unceasing photon strikes, mismatches between observed DIBs and experimental results, and the hitherto absence of DIBs matching any similarly sized cations. The putative gap in bottom-up synthesis is reaffirmed (diffuse ISM), and although DIB sources are largely unknown, within a broader approach the lines can help benchmark astrochemistry paradigms. The results relied on new advantageous Daly et al. experimental spectra, an expanded observational DIB analysis (APO catalog), and complementary $\omega$B97X-D/cc-pVTZ computations.

astro-ph.GA↗
arXiv2025

The Critical 9365 {\AA} Diffuse Interstellar Band and C$_{60}^{+}$ Association

The detection of interstellar C$_{60}^{+}$ has been debated for 30 years. The contested attribution of a weaker DIB at 9365 {\AA} was re-evaluated here on the basis of a Pearson correlation relative to 9577 {\AA}, which was previously tied to C$_{60}^{+}$ by diverse collaborations. An assessment of 11 sightlines revealed a high correlation amongst 9365$-$9577 {\AA} equivalent widths ($r=0.93 \pm 0.05$), after contamination from an adjacent line was mitigated using both numerical integration and Gaussian fits. In tandem with a recent separate study's high-$r$ evaluation linking 9577$-$9632 {\AA} across a sizable baseline: three interrelated DIBs matching C$_{60}^{+}$ laboratory findings were independently reaffirmed (9365, 9577, 9632 {\AA}). Yet further investigations are required to strengthen the case via two other weak DIBs disputedly linked to C$_{60}^{+}$, particularly owing to potential overlapping lines arising from an expansive chemical space (PAHs).

astro-ph.GA↗
arXiv2025

Potential Vibrational Modes Tied to Diffuse Interstellar Bands

Potential vibrational modes associated with diffuse interstellar bands (DIBs) could be discerned by examining energy differences between correlated DIBs. Consequently, $\approx 10^3$ higher correlated DIB pairs ($r-\sigma_r \ge 0.8$, $\ge 12$ sightlines) were extracted from the Apache Point Observatory DIB catalog, and their energy spacings computed. In this first macro exploratory step, a histogram possibly reveals chemical bond signatures of C$\equiv$C, C$\equiv$N, S$-$H, C$-$O, C$=$O, Si$-$H, N$-$H, C$-$H (aliphatic), C$\mathbf{^{\underline{...}}}$C (in-ring), and aromatics (C$-$H stretch, C$\mathbf{^{\underline{...}}}$C in-ring, oop C$-$H bending, and overtones). Continued research is required to (in)validate the histogram approach, mitigate noise, scrutinize maxima, break degeneracies, and converge upon an optimal framework.

astro-ph.GA↗
arXiv2025

Strengthening the Link Between Fullerenes and a Subset of Diffuse Interstellar Bands

A debate persists regarding the correlation between the DIBs 9577 and 9632 \r{A}, and whether they share a common molecular carrier (i.e., C$_{60}^{+}$). A robust high correlation determination emerges after bridging the baseline across an order of magnitude ($\simeq 50 - 700$ m\r{A}, $r=0.93\pm0.02$), and nearly doubling the important higher equivalent width domain by adding new Mg II-corrected sightlines. Moreover, additional evidence is presented of possible DIB linkages to fullerenes, whereby attention is drawn to DIBs at 7470.38, 7558.44, and 7581.47 \r{A}, which match the Campbell experimental results for C$_{70}^{+}$ within 1 \r{A}, and the same is true of 6926.48 and 7030.26 \r{A} for C$_{70}^{2+}$. Yet their current correlation uncertainties are unsatisfactory and exacerbated by expectedly low EWs (e.g., $\overline{EW}=4$ m\r{A} for 6926.48 \r{A}), and thus further observations are required to assess whether they represent a bona fide connection or numerical coincidence.

astro-ph.GA↗
arXiv2021

Quantum Crystallography N-Representability

Linus Pauling contributions span structural biology, chemistry in its broadest definition, quantum mechanical theory, valence bond theory, and even nuclear physics. A principal tool developed and used by Pauling is Xray, and electron, diffraction. One possible extension of the Pauling oeuvre could be the marriage of crystallography and quantum mechanics. Such an effort dates back to the sixties and has now flourished into an entire subfield termed quantum crystallography. Quantum crystallography could be achieved through the application of Clinton equations to yield N-representable density matrices consistent with experimental data. The implementation of the Clinton equations is qualitatively different for small and for large systems. For a small system, quantum mechanics is extracted from Xray data while for a large system, the quantum mechanics is injected into the system. In both cases, Nrepresentability is imposed by the use of the Clinton equations.

quant-ph↗
arXiv2021

Quantum Crystallography: Projectors and kernel subspaces preserving N-representability

Consider a projector matrix P, representing the first order reduced density matrix in a basis of orthonormal atom-centric basis functions. A mathematical question arises, and that is, how to break P into its natural component kernel projector matrices, while preserving N-representability of P. The answer relies upon 2- projector triple products, P'jPP'j. The triple product solutions, applicable within the quantum crystallography of large molecules, are determined by a new form of the Clinton equations, which - in their original form - have long been used to ensure N-representability of density matrices consistent with X-ray diffraction scattering factors.

quant-ph↗
arXiv2019

Anionic hydrogen clusters as a source of diffuse interstellar bands (DIBs)

The sources behind numerous key diffuse interstellar bands (DIBs) remain elusive, and thus evidence is presented here that a family of seven anionic hydrogen atomic clusters (H(-)2n+1, n = 1 to 7) are pertinent contributors. Configuration interaction calculations show hat these charge-induced dipole clusters are stable at temperatures characteristic of the interstellar medium, and emerge from the most abundant element in the Universe. The clusters' spectra yield 25 absorption optical lines that align with observed DIBs to within the computational uncertainties. The absorption bands are due to excitations from the ground states of the clusters to metastable states.

astro-ph.GA↗
arXiv2005

Determination of Wave Function Functionals: The Constrained-Search--Variational Method

In a recent paper [Phys. Rev. Lett. \textbf{93}, 130401 (2004)], we proposed the idea of expanding the space of variations in variational calculations of the energy by considering the approximate wave function $ψ$ to be a functional of functions $ χ: ψ= ψ[χ]$ rather than a function. The space of variations is expanded because a search over the functions $χ$ can in principle lead to the true wave function. As the space of such variations is large, we proposed the constrained-search-- variational method whereby a constrained search is first performed over all functions $χ$ such that the wave function functional $ψ[χ]$ satisfies a physical constraint such as normalization or the Fermi-Coulomb hole sum rule, or leads to the known value of an observable such as the diamagnetic susceptibility, nuclear magnetic constant or Fermi contact term. A rigorous upper bound to the energy is then obtained by application of the variational principle. A key attribute of the method is that the wave function functional is accurate throughout space, in contrast to the standard variational method for which the wave function is accurate only in those regions of space contributing principally to the energy. In this paper we generalize the equations of the method to the determination of arbitrary Hermitian single-particle operators as applied to two-electron atomic and ionic systems. The description is general and applicable to both ground and excited states. A discussion on excited states in conjunction with the theorem of Theophilou is provided.

physics.chem-ph↗
arXiv2005

Determination of a Wave Function Functional

In this paper we propose the idea of expanding the space of variations in standard variational calculations for the energy by considering the wave function $ψ$ to be a functional of a set of functions $χ: ψ= ψ[χ]$, rather than a function. In this manner a greater flexibility to the structure of the wave function is achieved. A constrained search in a subspace over all functions $χ$ such that the wave function functional $ψ[χ]$ satisfies a constraint such as normalization or the Fermi-Coulomb hole charge sum rule, or the requirement that it lead to a physical observable such as the density, diamagnetic susceptibility, etc. is then performed. A rigorous upper bound to the energy is subsequently obtained by variational minimization with respect to the parameters in the approximate wave function functional. Hence, the terminology, the constrained-search variational method. The \emph{rigorous} construction of such a constrained-search--variational wave function functional is demonstrated by example of the ground state of the Helium atom.

physics.atom-ph↗
arXiv2005

Bijectivity of the Normalization and Fermi-Coulomb Hole Sum Rules for Approximate Wave Functions

We prove the bijectivity of the constraints of normalization and of the Fermi-Coulomb hole charge sum rule at each electron position for approximate wave functions. This bijectivity is surprising in light of the fact that normalization depends upon the probability of finding an electron at some position, whereas the Fermi-Coulomb hole sum rule depends on the probability of two electrons staying apart because of correlations due to the Pauli exclusion principle and Coulomb repulsion. We further demonstrate the bijectivity of these sum rules by example.

physics.chem-ph↗
arXiv2005

The constrained-search--variational method: application to the ground state of Helium atom

n a recent paper we proposed the expansion of the space of variations in energy calculations by considering the approximate wave function $ψ$ to be a functional of functions $χ: ψ= ψ[χ]$ rather than a function. For the determination of such a wave function functional, a constrained search is first performed over the subspace of all functions $χ$ such that $ψ[χ]$ satisfies a physical constraint or leads to the known value of an observable. A rigorous upper bound to the energy is then obtained by application of the variational principle. To demonstrate the advantages of the expansion of variational space, we apply the constrained-search--variational method to the ground state of the negative ion of atomic Hydrogen, the Helium atom, and its isoelectronic sequence. The method is equally applicable to excited states, and its extension to such states in conjunction with the theorem of Theophilou is also described.

physics.atom-ph↗
arXiv2004

On the Hylleraas Coordinates

The Hylleraas coordinates $s=r_{1}+r_{2}$, $t=r_{1}-r_{2}$, $u=|{\bf r}_{1}-{\bf r}_{2}|$ are the natural coordinates for the determination of properties of the Helium atom, the positive ions of its isoelectronic sequence, and the negative Hydrogen ion. In this paper, we derive a new expression for integrals representing properties such as the energy, normalization and expectation of arbitrary operators, as written in the $(s,t,u)$ coordinates. The expression derived is valid for both \emph{finite} and \emph{infinite} space. The integrals for the various properties are comprised in each case of two components $A$ and $B$. The contribution of these components to the volume of integration and the normalization of a wave function for finite space, and in variational calculations of the ground state energy of the Helium atom confined in a finite volume is demonstrated by example. We prove that when the integration space is \emph{infinite}, the expression for the energy and other properties employed by Hylleraas corresponds \emph{only} to that of integral $A$. We further prove that for the approximate variational wave functions employed by Hylleraas and other authors, the contribution of the term $B$ vanishes. This contribution also vanishes for the exact wave function. It is interesting to note that the component $B$ to the integral is not mentioned in the literature. A principle purpose of the paper, therefore, is to point out the existence of this term.

physics.atom-ph↗