kth.sePublications
Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Size-dependent polarizabilities and van der Waals dispersion coefficients of fullerenes from large-scale complex polarization propagator calculations
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Theoretical Chemistry and Biology. KTH Royal Inst Technol, Dept Theoret Chem & Biol, Sch Engn Sci Chem Biotechnol & Hlth, SE-10691 Stockholm, Sweden..ORCID iD: 0000-0003-3992-043X
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Theoretical Chemistry and Biology. KTH Royal Inst Technol, Dept Theoret Chem & Biol, Sch Engn Sci Chem Biotechnol & Hlth, SE-10691 Stockholm, Sweden..ORCID iD: 0000-0002-8707-3733
KTH, School of Electrical Engineering and Computer Science (EECS), Centres, Centre for High Performance Computing, PDC. KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Theoretical Chemistry and Biology. KTH Royal Inst Technol, Dept Theoret Chem & Biol, Sch Engn Sci Chem Biotechnol & Hlth, SE-10691 Stockholm, Sweden..ORCID iD: 0000-0001-6508-8355
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Theoretical Chemistry and Biology. Department of Physics, Faculty of Mathematics and Natural Sciences, Kaunas University of Technology, LT-51368 Kaunas, Lithuania.ORCID iD: 0000-0003-2729-0290
Show others and affiliations
2021 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 154, no 7, article id 074304Article in journal (Refereed) Published
Abstract [en]

While the anomalous non-additive size-dependencies of static dipole polarizabilities and van der Waals C-6 dispersion coefficients of carbon fullerenes are well established, the widespread reported scalings for the latter (ranging from N-2.2 to N-2.8) call for a comprehensive first-principles investigation. With a highly efficient implementation of the linear complex polarization propagator, we have performed Hartree-Fock and Kohn-Sham density functional theory calculations of the frequency-dependent polarizabilities for fullerenes consisting of up to 540 carbon atoms. Our results for the static polarizabilities and C-6 coefficients show scalings of N-1.2 and N-2.2, respectively, thereby deviating significantly from the previously reported values obtained with the use of semi-classical/empirical methods. Arguably, our reported values are the most accurate to date as they represent the first ab initio or first-principles treatment of fullerenes up to a convincing system size.

Place, publisher, year, edition, pages
AMER INST PHYSICS , 2021. Vol. 154, no 7, article id 074304
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-292491DOI: 10.1063/5.0040009ISI: 000630521400004PubMedID: 33607910Scopus ID: 2-s2.0-85100915441OAI: oai:DiVA.org:kth-292491DiVA, id: diva2:1543471
Note

QC 20210412

Available from: 2021-04-12 Created: 2021-04-12 Last updated: 2022-10-17Bibliographically approved
In thesis
1. Implementation of complex polarization propagator theory for linear response properties of large molecular systems
Open this publication in new window or tab >>Implementation of complex polarization propagator theory for linear response properties of large molecular systems
2022 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Since its beginning, the remarkable development from the first commercially available computers toward exascale supercomputers just within the span of a lifetime has been closely intertwined with the perpetual quest for the utilization of the arising computing power for the avail of theoretical chemistry. With the aim of further pushing the limits of computationally accessible molecular system sizes, this thesis includes the presentation of programming efforts, which brought forth two quantum chemical software codes, as well as a range of ab initio studies on carbon-based systems, enabled by the former.

The VeloxChem and Gator programs, developed for spectroscopy simulations at the level of density-functional theory (DFT) and correlated wave function methods, respectively, employ a hybrid message passing interface (MPI)/open multiprocessing (OpenMP) parallelization scheme embedded in a modular program structure written in a Python/C++ layered fashion for the execution in contemporary high-performance computing (HPC) environments. Included numerical solvers for the evaluation of real and complex linear response functions in combination with the parallel construction of auxiliary Fock matrices enable the efficient calculation of one-photon absorption or electronic circular dichroism (CD) spectra in the ultraviolet/visible (UV/vis) or X-ray spectral region, as well as van der Waals C6 dispersion coefficients.

Employing the VeloxChem program in two comprehensive investigations, the C6 dispersion coefficients of carbon fullerenes up to a system size of C540 and the CD spectra of carbohelicenes ranging from CH[5] to CH[30] have been calculated at the DFT level of theory. The revealed non-additive scaling with respect to the number of carbon atoms of N2.2 in the former and nontrivial CD band progressions, arguably linked to the number of overlapping layers in the helical conjugated systems, in the latter rectify the current conception in their respective fields.

In a benchmark for the Gator program on a series of guanine oligomers, the full UV/vis spectrum for a tetrad was calculated at the level of a second-order algebraic-diagrammatic construction (ADC(2)) scheme in just under 15 hours by efficient employment of 32,768 central processing unit (CPU) cores.

Exceeding the limit of 10,000 and 1,000 contracted basis functions for a treatment with the DFT and ADC(2) methods, respectively, these practical examples demonstrate the capability of VeloxChem and Gator to harness vast computational resources made available by contemporary and future HPC systems and thereby routinely address scopes of system sizes that were previously out of reach.

Abstract [sv]

Den anmärkningsvärda utvecklingen som inom enbart loppet av en livstid gått från de första kommersiellt tillgängliga datorerna mot exascale superdatorer har varit nära sammanflätad med en strävan att kunna utnyttja den uppgraderade beräkningskraften för att kunna lösa mer komplexa problem inom den teoretisk kemin. I syfte att ytterligare tänja på gränserna för beräkningsmässigt tillgängliga molekylära systemstorlekar, inkluderar denna avhandling en presentation av programmeringsinsatser som ledde till utvecklingen av två kvantkemiska mjukvarukoder, såväl som en rad ab initio studier på kolbaserade system, där de två mjukvarukoderna applicerades.

VeloxChem- och Gator-programmen som är utvecklade för spektroskopi-simuleringar på nivån för density-functional theory (DFT) respektive korrelerade vågfunktionsmetoder, använder ett hybrid-message passing interface (MPI)/open multiprocessing (OpenMP) parallelliseringsschema som är inbäddat i en modulär programstruktur skriven i lager av  Python/C++ för exekvering i nutida hög-prestandaberäkningsmiljöer (HPC). De inkluderade numeriska lösningsalgoritmerna för utvärdering av reella och komplexa linjära responsfunktioner i kombination med den parallella konstruktionen av extra Fock-matriser möjliggör effektiv beräkning av både en-fotonabsorption eller elektronisk cirkulär dikroism (CD)-spektra i ultravioletta/synliga (UV/vis) eller röntgen områden, samt beräkningar av van der Waals C6 dispersionskoefficienter.

Genom att använda VeloxChem-programmet i två omfattande undersökningar har dispersionskoefficienterna C6 för kolfullerener upp till en systemstorlek på C540 och CD-spektra av kolhelicener från CH[5] till CH[30] varit beräknade på DFT-nivå. Den första undersökningen avslöjade en icke-additiv skalning med avseende på antalet kolatomer av N2,2. Den andra identifierade icke-triviala CD-bandprogressioner, som förmodligen är kopplat till antalet överlappande lager i de spiralformade konjugerade systemen. Resultaten från dessa studier utmanar den nuvarande uppfattningen inom undersökningarnas respektive områden.

I en jämförelse på en serie guanin-oligomerer utförda med Gator-programmet, beräknades hela UV/vis-spektrumet för en tetrad på nivån av ett andra-ordningens algebraic-diagrammatic construction (ADC(2)) scheme på mindre än 15 timmar genom effektivt nyttjande av 32 768 kärnor för centralprocessorer (CPU).

Genom att överskrida gränsen på 10 000 och 1 000 kontrakterade basfunktioner för en behandling med DFT- respektive ADC(2)-metoderna, visar dessa applicerade exempel på VeloxChems och Gators förmåga att utnyttja enorma beräkningsresurser som görs tillgängliga av både nutida och framtida HPC-system och därmed tillåter rutinmässiga beräkningar av systemstorlekar som tidigare var utom räckhåll.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2022. p. 87
Series
TRITA-CBH-FOU ; 2022:54
National Category
Theoretical Chemistry
Research subject
Theoretical Chemistry and Biology
Identifiers
urn:nbn:se:kth:diva-320270 (URN)978-91-8040-394-8 (ISBN)
Public defence
2022-11-18, D37, Lindstedtsvägen 5, Zoom: https://kth-se.zoom.us/j/67595336394, Stockholm, 09:00 (English)
Opponent
Supervisors
Note

QC 2022-10-18

Available from: 2022-10-18 Created: 2022-10-17 Last updated: 2022-11-16Bibliographically approved

Open Access in DiVA

No full text in DiVA

Other links

Publisher's full textPubMedScopus

Authority records

Brand, ManuelAhmadzadeh, KaranLi, XinRinkevicius, ZilvinasNorman, Patrick

Search in DiVA

By author/editor
Brand, ManuelAhmadzadeh, KaranLi, XinRinkevicius, ZilvinasSaidi, Wissam A.Norman, Patrick
By organisation
Theoretical Chemistry and BiologyCentre for High Performance Computing, PDC
In the same journal
Journal of Chemical Physics
Theoretical Chemistry

Search outside of DiVA

GoogleGoogle Scholar

doi
pubmed
urn-nbn

Altmetric score

doi
pubmed
urn-nbn
Total: 129 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf