- Computational Chemistry
TUNNEX: An easy-to-use Wentzel-Kramer-Brillouin (WKB) implementation to compute tunneling half-lives. Hendrik Quanz and Peter R. Schreiner
J. Comput. Chem. 2019, 41, 543-547.
Tunneling in experiments (TUNNEX) is a free open‐source program with an easy‐to‐use graphical user interface to simplify the process of Wentzel‐Kramers‐Brillouin (WKB) computations. TUNNEX aims at experimental chemists with basic knowledge of computational chemistry, and it offers the computation of tunneling half‐lives, visualization of data, and exporting of graphs. It also provides a helper tool for executing the zero‐point vibrational energy correction along the path. The program also enables computing high‐level single points along the intrinsic reaction path. TUNNEX is available at https://github.com/prs-group/TUNNEX. As the WKB approximation usually overestimates tunneling half‐lives, it can be used to screen tunneling processes before proceeding with elaborate kinetic experiments or higher‐level tunneling computations such as instanton theory and small curvature tunneling approaches. © 2018 Wiley Periodicals, Inc.
Computational Chemistry: The fate of current methods and future challenges. Stefan Grimme and Peter R. Schreiner
Angew. Chem. Int. Ed. 2018, 57, 4170–4176. Angew. Chem. 2018, 130, 4241–4248.
“Where do we go from here?” is the underlying question regarding the future (perhaps foreseeable) developments in computational chemistry. Although this young discipline has already permeated practically all of chemistry, it is likely to become even more powerful with the rapid development of computational hard‐ and software.
Polytriangulane. Wesley D. Allen, Henrik Quanz, and Peter R. Schreiner
J. Chem. Theory Comput. 2016, 12, 4707–4716.
Heats of formation of platonic hydrocarbon cages by means of high-level thermochemical procedures.
Amir Karton, Peter R. Schreiner and Jan M. L. Martin
J. Comput. Chem. 2016, 37, 49–58.
Nature Utilizes Unusual High London Dispersion Interactions for Compact Membranes Comprised of Molecular Ladders. J. Philipp Wagner and Peter R. Schreiner* J. Chem. Theory Comput. 2014, 10, 1353–1358. DOI: 10.1021/ct5000499
London dispersion interactions play a key role in nature, in particular, in membranes that constitute natural barriers. Here we demonstrate that the spatial alignment of “molecular ladders” ([n]ladderanes), i.e., highly unusual and strained all-trans-fused cyclobutane moieties, leads to much larger attractive dispersion interactions as compared to alkyl chains of the same length. This provides a rationale for the occurrence of peculiar ladderane fatty acids in the dense cell walls of anammox bacteria. Despite the energetic penalty paid for the assembly of such strained polycycles, the advantage lies in significantly higher, dispersion-dominated interaction energies as compared to straight-chain hydrocarbon moieties commonly found in fatty acids. We discern the dispersion contributions to the total interaction energies using a variety of computational methods including modern dispersion-corrected density functional theory and high level ab initio approaches. Utilizing larger assemblies, we also show that the intermolecular interactions behave additively.
Combined ab initio molecular dynamics and experimental studies show that carbon atom addition to benzene. Michael L. McKee,* Hans-Peter Reisenauer, and Peter R. Schreiner,* J. Phys. Chem. A. 2014, 118, in press. DOI: dx.doi.org/10.1021/jp501107b
Car–Parrinello molecular dynamics was used to explore the reactions between triplet and singlet carbon atoms with benzene. The computations reveal that, in the singlet C atom reaction, products are very exothermic where nearly every collision yields a product that is determined by the initial encounter geometry. The singlet C atom reaction does not follow the minimum energy path because the bimolecular reaction is controlled by dynamics (i.e., initial orientation of encounter). On the other hand, in a 10 K solid Ar matrix, ground state C(3P) atoms do tend to follow RRKM kinetics. Thus, ab initio molecular dynamics (AIMD) results indicate that a significant fraction of C–H insertion occurs to form phenylcarbene whereas, in marked contrast to previous theoretical and experimental conclusions, the Ar matrix isolation studies indicate a large fraction of direct cycloheptatetraene formation, without the intermediacy of phenylcarbene. The AIMD calculations are more consistent with vaporized carbon atom experiments where labeling studies indicate the initial formation of phenylcarbene. This underlines that the availability of thermodynamic sinks can completely alter the observed reaction dynamics.
Polytwistane. Shiblee Barua, Henrik Quanz, Martin Olbrich, Peter R. Schreiner, Dirk Trauner, and Wesley D. Allen* Chem. Eur. J. 2014, 20, 1638–1645. DOI: 10.1002/chem.201303081.
Twistane, C10H16, is a classic D2-symmetric chiral hydrocarbon that has been studied for decades due to its fascinating stereochemical and thermodynamic properties. Here we propose and analyze in detail the contiguous linear extension of twistane with ethano (ethane-1,2-diyl) bridges to create a new chiral, C2-symmetric hydrocarbon nanotube called polytwistane. Polytwistane, (CH)n, has the same molecular formula as polyacetylene but is composed purely of C(sp3)H units, all of which are chemically equivalent. The polytwistane nanotube has the smallest inner diameter (2.6 Å) of hydrocarbons considered to date. A rigorous topological analysis of idealized polytwistane and a C236H242 prototype optimized by B3LYP density functional theory reveals that the polymer has a nonrepeating, alternating σ-helix, with an irrational periodicity parameter and an instantaneous rise (or lead) angle near 15 °. A theoretical analysis utilizing homodesmotic equations and explicit computations as high as CCSD(T)/cc-pVQZ yields the enthalpies of formation (twistane)=−1.7 kcal mol−1 and (polytwistane)= +1.28 kcal (mol CH)−1, demonstrating that the hypothetical formation of polytwistane from acetylene is highly exothermic. Hence, polytwistane is synthetically viable both on thermodynamic grounds and also because no obvious pathways exist for its rearrangement to lower-lying isomers. The present analysis should facilitate the preparation and characterization of this new chiral hydrocarbon nanotube.
Steric crowding can stabilize a labile molecule: Solving the hexaphenylethane riddle. Stefan Grimme* and Peter R. Schreiner*
Angew. Chem. Int. Ed. 2011, 50, 12639–12642. Angew. Chem. 2011, 123, 12849–12853. Download Highlight: Nachr. Chem. 2012, 60, 108.
Abstract. 12 not so angry men: Hexaphenylethane is unstable, a phenomenon traditionally attributed to steric repulsion between the six phenyl rings. However, adding 12 bulky tert-butyl groups, one to each of the 12 meta positions, gives a stabile ethane derivative (see space-filling model and potential energy curve for the dissociation of the central CC bond). This unexpected stabilization is shown to result from attractive dispersion interactions between the substituents.
σ/σ- and π/π-Interactions are Equally important: Multilayered Graphanes. Andrey A. Fokin,* Dennis Gerbig, and Peter R. Schreiner*
J. Am. Chem. Soc. 2011, 133, 20036–20039. Download
Abstract. The properties of single-sheet [n]graphanes, their double-layered forms (diamondoids), and their van der Waals (vdW) complexes (multilayered [n]graphanes) were studied for n = 10–97 at the dispersion-corrected density functional theory (DFT) level utilizing B97D with a 6-31G(d,p) basis set; for comparison, we also computed a series of structures at M06-2X/6-31G(d,p) as well as B3LYP-D3/6-31G(d,p) and evaluated SCS-MP2/cc-pVDZ single-point energies. The association energies for the vdW complexes reach 120 kcal mol–1 already at 2 nm particle size (graphane dimer), and graphanes adopt layered structures similar to that of graphenes. The association energies of multilayered graphanes per carbon atom are rather similar and independent of the number of layers (ca. 1.2 kcal mol–1). Graphanes show quantum confinement effects as the HOMO–LUMO gaps decrease from 8.2 eV for graphane to 5.7 eV for graphane, asymptotically approaching 5.4 eV previously obtained for bulk graphane. Similar trends were found for layered graphanes, where the differences in the electronic properties of double-sheet CH/σ vdW and double-layered CC/σ diamondoids vanish at particles sizes of 1 nm. For comparison, we studied the parent CC/π systems, i.e., the single- and double-sheet [n]graphenes (n = 10–130) for which the association energies demonstrate the same trends as in the case of [n]graphanes; in both cases the band gaps decrease with an increase in system size. The graphene dimer (HOMO–LUMO gap = 0.5 eV) already approaches the 2D metallic properties of graphite.
Understanding the Torquoselectivity in 8π-Electrocyclic Cascade Reactions: Synthesis of Fenestradienes versus Cyclooctatrienes. Catherine Hulot, Shadi Amiri,Gaëlle Blond, Peter R. Schreiner, and Jean Suffert.
J. Am. Chem. Soc. 2009, 131, 13387. Download
Abstract. Unusual and novel polycyclic cyclooctatrienes, fenestradienes, and fenestrenes form readily from trienynes depending on the structure of the starting trienynes and the reaction conditions. The experimentally observed high torquoselectivities and complete diastereoselectivities of the 8π-electrocyclization products have been thoroughly studied using density functional computations at B3PW91/6-31g(d,p). The different P- and M-helical topologies for the Möbius aromatic transition structures are the origin of the observed torquoselectivities in the cyclooctatrienes. The P-helical topologies direct the newly formed single bonds into a favorable equatorial position of the neighboring cycloalkane moieties (X = ring size) that retain their most stable conformation. The M-helical transition structures lead to an axial connection for the smaller rings (X = 4–6) and an equatorial connection for the seven- and eight-membered cycloalkanes. This leads to unfavorable conformations for the larger cycloalkane moieties. Experiments and computations show that for trienynes involving small neighboring cycloalkane groups (X = 4–6) M-helical topology is preferred toward cyclooctatrienes and in the following the corresponding fenestradienes can be formed as kinetic or even thermodynamic products; they convert to their more stable cyclooctatriene valence isomers derived from P-helical transition structures at higher temperatures. For larger cycloalkane moieties with more conformational flexibility only cyclooctatrienes with torquoselectivities derived from P-helical transition structures form.
Non-Kekulé N-Substituted m-Phenylenes: N-Centered Diradicals versus Zwitterions. Shadi Amiri, Peter R. Schreiner* J. Phys. Chem. 2009, 113, 11750–11757. Download
Abstract. The relationship between the structures and electronic ground state properties of non-Kekulé-type N-substituted m-phenylenes was studied utilizing density functional theory (DFT), with the aim of determining the factors that lead to ground state triplet diradicals. At B3LYP/6-311G(d,p)//B3LYP/6-311G(d,p) we identified octahydropyrido-quinoline with an exceptionally large singlet–triplet energy separation of +27.9 kcal mol–1, in favor of the triplet. The high-spin structures can readily be obtained by interruption of the full cyclic π-delocalization that avoids cross-conjugation of the nitrogen radical centers. Introduction of additional heteroatoms on the other hand preferentially stabilizes the singlet zwitterionic resonance contributors in these systems. The identified diradicals show strong ferromagnetic exchange interactions between two radical-centers.
3,5,7,9-Substituted Hexaazaacridines: Toward Structures with Nearly Degenerate Singlet-Triplet Energy Separations. Peter Langer,* Shadi Amiri, Anja Bodtke, Nehad Saleh, Klaus Weisz, Halmar Görls, and Peter R. Schreiner*
J. Org. Chem. 2008, 73, 5048. Download
Abstract. Toward the goal of preparing stable, neutral open-shell systems, we synthesized a novel series of p-phenylsubstituted 3,5,7,9-hexaazaacridine and 3,5,7,9-hexaazaanthracene derivatives. The effects of substitution on the molecular electronic properties were probed both experimentally and computationally [B3LYP/6-311G(d,p)//B3LYP/6-31G(d,p)]. While the experimentally prepared structures already have small (20–25 kcal/mol) singlet-triplet energy gaps, systems with even smaller (<9 kcal/mol) singlet-triplet energy separations can be realized through systematic variation of the substituent numbers, types, and patterns. Hexaazaanthracenes show generally smaller singlet-triplet energy gaps than hexaazaacridines. Nitrogenbonded σ- and π-acceptor substituents that cause positive inductive and mesomeric effects as well as carbon-bonded σ-donor substituents make substituted hexaazaanthracenes promising candidates for purely organic high-spin systems.