Actividad del Grupo de Química Teórica - UAM

Manuel Alcamí

Departamento de Química Universidad Autónoma de Madrid

IMDEA-Nanoscience

Madrid

Jornada científica NanoFrontMag 21 – Junio - 2016

Grupo Química Teórica - UAM

Composición del Grupo

Fernando Martín

Sergio Diaz-Tendero Investigador RyC

Yang Wang Ayudante doctor

Manuel Alcamí

Cristina Díaz Investigadora RyC

Michelle Pisarra Contrato Postdoctoral

Daniele Stradi QuantumWise A/S

Maitreyi Robledo Technische U. Berlin

Paula Pla FPU

Fernando Aguilar-Galindo FPI

Jinggang Lan EM - Master

Temas de Trabajo

-  Autoensamblado de moléculas en superficies

-  Grafeno sobre superficies metálicas – S intercalado G / Ru(0001) -  Catálisis de NO

-  Fullerenos

-  Antimoneno

NanoFrontMag Temas

TCNQ / Cu(111) NanoFrontMag Autoensamblado

T Control of self-assembly

D. Stradi, B. Borca, S. Barja, M. Garnica, C. Díaz, J.M. Rodríguez-García, M. Alcamí, A.L. Vázquez de Parga, R. Miranda and F. Martín RSC Advances 6, 15071-15079 (2016)

Deposition room T Anneling 350 K

Deposition 350 K

Theoretical results Two almost degenerate configurations

Structure of isolated molecules – strong interaction with surface

Self-assembly patters mixtures of T1 and T2 configurations

TCNQ / Ag(111) | TTF / Ag(111) | TTF+TCNQ / Ag(111) NanoFrontMag Autoensamblado

Self-assembly patterns

M. Robledo, F. Martín, S. Díaz-Tendero, M. Alcamí Experimental: R. Otero, R. Miranda Tesis M. Robledo (Junio 2015)

TCNQ / Ag(111)

Charge transfer -1.15 e- / molecule

TTF / Ag(111)

+ 0.011 e- / molecule +0.056 +0.073 e- /molecule

TTF+TCNQ / Ag(111) NanoFrontMag Autoensamblado

M. Robledo, F. Martín, S. Díaz-Tendero, M. Alcamí Experimental: R. Otero, R. Miranda Tesis M. Robledo (Junio 2015)

TTF+TCNQ / Ag(111) NanoFrontMag Autoensamblado

M. Robledo, F. Martín, S. Díaz-Tendero, M. Alcamí Experimental: R. Otero, R. Miranda Tesis M. Robledo (Junio 2015)

Gd-Carboxilate coordination networks NanoFrontMag Autoensamblado

J. Urgel, B. Cirera, Y. Wang, W. Auwärter, R. Otero, J.M. Gallego, M. Alcami, S. Klyatskaya, M. Ruben, F. Martin, R. Miranda, D. Ecija and J. Barth Small 11, 6358-6364 (2015)

Gd + TDA / Cu(111)

Structure thermally Robust

-Binding energy 4.99 eV / molecule - Planar phenylene - Large coordination of Gd (8 O) Rotation carboxylate groups 44.5 º

Fe-DCNQI coordination networks NanoFrontMag Autoensamblado

J. Rodríguez-Fernández Y. Wang, M. Alcami, F. Martin, R. Otero, J.M. Gallego and R. Miranda J. Phys. Chem. C (Submitted) Fe (II) + DCNQI / Ag(111)

N

NC

C

N

N

DCNQI / Ag(111) Fe (II) + DCNQI / Ag(111)

320 K 380 K

a)

b)

c)

Geometry and Charge distributions DFT –PBE- (3,3,1) 4 Ag layers

Charge: Fe (+1.20) + DCNQI (-1.14) Magnetic moment Fe 1.74 µB

Charge: Fe (+1.36) + DCNQI (-0.68)

S-intercalado Grafeno-Ru(0001)

NanoFrontMag Grafeno

M. Pisarra, C. Diaz, F. Martín Exp: A. López de Parga, R. Miranda

4 fases S Ru(0001)

Grafeno / S Ru(0001)

Interacción grafeno-superficie debil (𝑑 > 3Å) 𝑑𝑝(2×2)≈3.0Å 𝑑𝑝(√3×√3)≈3.3Å

𝑑𝐷𝑊𝑐𝑝≈3.3Å 𝑑𝑐(2×4)≈3.3Å Moirè Pattern

d𝑝(2×2) 0.09Å 𝑑𝑝(√3×√3):0.02Å d𝐷𝑊𝑐𝑝:0.05Å 𝑑𝑐(2×4):0.05Å

S-intercalado Grafeno-Ru(0001)

NanoFrontMag Grafeno

Estructura de bandas S Ru(0001) Phys Rev B (en preparación)

NO Catalytic dissociation over Ru NanoFrontMag NO- Catalysis

Jinggang Lan. Y. Wang, M. Alcamí, F. Martín Experimental: R. Otero, R. Miranda Master Thesis work

Surface (101) NO adsorption

N & O adsorption

NO dissociation

N & O atomic chemisorption and diffusion

Structure of charged fullerenes NanoFrontMag Fullerenes

Y. Wang, S. Díaz-Tendero, M. Alcamí, F. Martín Nature Chemistry, 7. 927-934 (2015) J. Am. Chem. Soc. 138, 1551-1560 (2016).

Charged Fullerenes Endohedral MetalloFullerenes (EMFs) Mq+@Cn

q-

Number Structural Isomers C60X8 418.470 / C60X18 7.7 1012

Y.-Z. Tan, et al. Nature Chem. 1, 450 (2009)

C60 C56Cl10

C64Cl4

Exofullerenes: C2nX2m X=H, F, Cl, Br, CF3

Number Structural Isomers C60 1812 / C120 1.671.471

Structure of endofullerenes NanoFrontMag Fullerenes

Y. Wang, S. Díaz-Tendero, M. Alcamí, F. Martín Nature Chemistry, 7. 927-934 (2015) J. Am. Chem. Soc. 138, 1551-1560 (2016) Phys. Chem. Chem. Phys. In press (2016).

Methodology based in extremely simple calculations to predict relative stability isomers Parameter: ΔCSI - Charge Stabilization Index - Changes in electronic (π cloud) stability with respect neutral - Structural train effects (pentagon-pentagon bonds) Allowed us to explore around 3 millions possible structures Identify the key factors governing fullerene stabilities

Structural motifs, aromaticity…

Y.-Z. Tan, et al. Nature Chem. 1, 450 (2009)

Invited talks - ECAMP - HCI - Spanish-Japanese workshop

Antimonene NanoFrontMag Antimonene

P. Ares, F. Aguilar-Galindo, D. Rodriguez-San-Miguel, S. Díaz-Tendero, M. Alcamí, F. Martín, J. Gómez-Herrero and F. Zamora Mechanical Isolation of Highly Stable Antimonene under Ambient Conditions Adv. Mater. (Early view 2016)

Single/few-layer antimony flakes

Simulations Dynamics room T / Solvation effects

Electronic structure 1 monolayer - Bandgap in vacuum for 1 ML is 1.6 eV, - Bandgap closes with T or solvent